Synthesis and reactivity of new functionalized perfluoroalkylfluorophosphates.

DOI: 10.1002/chem.201402421

Full Paper

& Fluorine Chemistry

Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates Nadine Allefeld,[a] Beate Neumann,[a] Hans-Georg Stammler,[a] Gerd-Volker Rçschenthaler,[b] Nikolai Ignat’ev,[c] and Berthold Hoge*[a] Dedicated to Prof. Lothar Weber on the occasion of his 70th birthday

gen—a structural characterization was achieved from the CF3 analogue. Reaction of [(C2F5)3F2P(CH2NMe CH2NMe3)] and PMe3 gave rise to the formation of the zwitterionic phosphonium phosphate [(C2F5)3F2P(CH2NMe CH2PMe3)], which was fully characterized by X-ray diffraction analysis. Moreover, an efficient one-pot synthesis of Cs + [(C2F5)3F2P(CH2NMe2)] was pursued. This salt turned out to be a useful nucleophile in several alkylation reactions.

Abstract: A new efficient synthesis of functionalized perfluoroalkyl fluorophosphates by oxidative addition of Me2NCH2F to the electron-deficient phosphanes (C2F5)nPF3 n (n = 0–3) is reported. The initially formed zwitterionic, hexacoordinated phosphates [(C2F5)nF5 nP(CH2NMe2 CH2NMe2)] are converted into the corresponding phosphonium salts [(Me3PCH2NMe2] + [(C2F5)nF5 nP(CH2NMe2)] by treatment with PMe3. In addition [(C2F5)3F2P(CH2NMe2 CH2NMe2)] can undergo a 1,3-methyl shift from the internal to the terminal nitro-

Introduction

alkoxy-FAP in [(C2F5)3F2POR] .[9] The precursor (C2F5)3PF2 is available in multikilogram quantities by means of electrochemical fluorination of P(C2H5)3 in anhydrous hydrogen fluoride.[10] In general partially fluorinated phosphorus(V) compounds are accessible by oxidation of the corresponding phosphanes with elemental fluorine or SbF3 in a coupled halogen-exchange redox reaction.[11] However, the handling of elemental fluorine requires special experience and safety precautions. A safer method is based upon the oxidation with elemental chlorine and the subsequent reaction with fluorination agents.[12] Rçschenthaler et al. presented in 2012 another protocol for electron-poor, hexacoordinated phosphorus(V) compounds. The oxidative addition of 2,2-difluorobis(dialkylamines) to phosphorus(III) halides led to the formation of carbene-coordinated complexes of phosphorus(V) fluorides.[13] A similar reactivity can be expected from fluoromethyldimethylamine. From the first reported synthesis in 1970[14] until today, fluoromethyldimethylamine has been intensely studied as an example for negative hyperconjugation. In contrast to the salt-like structure of the chloro, bromo, and iodo derivatives, fluoromethyldimethylamine is a volatile and colorless liquid at room temperature, indicating a covalent C F bond. Nonetheless, donation of the nitrogen lone pair into the antibonding s* orbital of the C F bond can be assumed, which is expressed by the ionic resonance structure shown in Equation (1). The destabilization of the C F bond causes an interesting reactivity. In the presence of strong elec-

Phosphates play an important role not only in biological processes, but also in the production of electronic devices. A prominent example is lithium hexafluorophosphate Li + [PF6] , which is a commercially used electrolyte for lithium-ion batteries.[1] A major disadvantage of Li + [PF6] is its sensitivity towards moisture. Hydrolysis leads to the liberation of toxic and aggressive hydrogen fluoride.[2] Compared with [PF6] , tris(pentafluoro)trifluorophosphate (FAP), [(C2F5)3PF3] , possesses three sterically demanding and electron-withdrawing pentafluoroethyl groups, leading to a decreased sensitivity towards moisture and an increased thermal stability. LiF addition to the strong Lewis acid (C2F5)3PF2 affords Li + [FAP] .[3] In addition to the successful application in batteries,[4] FAP-based ionic liquids are used as components of electrolytes, field effect transistors,[5] or as additives for lubricants.[6] To date some variations in the FAP anions are known, that is, the hydride-FAP in [(C2F5)3F2PH] ,[7] chloride-FAP in [(C2F5)3F2PCl] ,[8] adducts of the type [(C2F5)3F2PD] (D = dimethylaminopyridine or DMF) and

[a] N. Allefeld, B. Neumann, Dr. H.-G. Stammler, Prof. Dr. B. Hoge Centrum fr Molekulare Materialien Fakultt fr Chemie, Anorganische Chemie Universitt Bielefeld, Universittsstrasse 25, 33615 Bielefeld (Germany) E-mail: [email protected] [b] Prof. Dr. G.-V. Rçschenthaler School of Engineering and Science Jacobs University Bremen, Campus-Ring 1, 28759 Bremen (Germany) [c] Dr. N. Ignat’ev Merck KGaA, PM-ATI Frankfurter Strasse 250, 64293 Darmstadt (Germany) Chem. Eur. J. 2014, 20, 1 – 11

These are not the final page numbers! ÞÞ

1

2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

&

&

Full Paper trophiles fluoride ions are liberated from fluoromethyldimethylamine.[15] Here we present the selective synthesis of novel, electrondeficient, functionalized phosphates. The products, which are obtained by the oxidative addition of fluoromethyldimethylamine to phosphanes, are fully characterized and their reactivity is explored.

troscopy. A similar mechanism was proposed by Rçschenthaler et al.[13] They reported the reaction of phosphorus(III) fluoride with 2,2-difluorobis(dialkylamines), which proceeds via a tetrafluorophosphoranide ion as an intermediate. Due to chemically inequivalent fluorine atoms, the 31P{1H} NMR spectrum reveals a doublet of quintets with 1J(P,F) coupling constants of 821 and 722 Hz, respectively. A further coupling of the phosphorus atom to the CH2 group shows a triplet in the proton coupled 31P NMR spectrum with a 2J(P,H) coupling constant of 17 Hz. Correspondingly, the proton NMR spectrum exhibits a doublet of quintets at 3.0 ppm with a 2J(P,H) coupling of 17 Hz and a 3J(F,H) coupling of 6 Hz to the fluorine atoms in the cis position. The signal for the CH2 group between the nitrogen atoms is observed at 4.0 ppm. Similarly the perfluoroalkyl-substituted phosphanes (Rf)nPF3 n (Rf = C2F5, n = 1–3) react with two equivalents of fluoromethyldimethylamine forming the zwitterionic derivatives 1 b–1 d. All compounds were isolated as colorless solids in good yield and characterized by 1H, 13C, 19F, and 31P NMR, IR spectroscopy and mass spectrometry (Table 1). The 31P NMR spectrum of

Results and Discussion Synthesis of [(C2F5)nF3 nP(CH2NMe2 CH2NMe2)] (n = 0–3) The reaction of phosphorus(III) fluoride with fluoromethyldimethylamine in diethyl ether led to the formation of a colorless solid. Based on NMR spectroscopic and mass spectrometric analyses, the product was identified as [F5P(CH2NMe2 CH2NMe2)] (1 a). A conceivable mechanism is depicted in Scheme 1.

Table 1. Selected

31

P and

19

1

139.9 140.9 146.3 155.0 147.2

821[a]/722[b] 908 889[c]/860[d] 826 870

d( P) [ppm] 1a 1b 1c 1d 3d

F NMR spectroscopic data of 1 a–1 d and 3 d.

31

J(P,F) [Hz]

d(19F) [ppm] 53.9[a]/ 67.3[b] 55.2 30.7[c]/ 77.1[d] 41.5 47.0

[a] 1 F. [b] 4 F. [c] 2 F. [d] 1 F.

[(C2F5)F4P(CH2NMe2 CH2NMe2)] (1 b) exhibits a quintet of triplets of triplets at 140.9 ppm. The quintet results from the coupling of the phosphorus to four chemically equivalent fluorine atoms confirming the trans geometry shown in Figure 1. The triplet of triplet splitting is due to the 2J(P,F) (104 Hz) and a 2J(P,H) coupling (18 Hz). Accordingly, the 31P NMR spectrum of [(C2F5)2F3P(CH2NMe2 CH2NMe2)] (1 c) exhibits a doublet of triplets of multiplets due to a 1J(P,F) = 889 Hz coupling to the fluorine atom trans to one pentafluoroethyl group and a 1J(P,F) = 860 Hz coupling to two other chemically equivalent fluorine atoms. The extensive coupling of the phosphorus

Scheme 1. Proposed mechanism for the reaction of fluoromethyldimethylamine with phosphorus(III) fluoride.

In the first step a fluoride ion is transferred from Me2NCH2F to the phosphane PF3 under formation of the corresponding phosphoranide, [PF4] ,[16] and an iminium ion, [Me2NCH2] + . In the following step the nucleophilic phosphoranide ion attacks the electrophilic iminium carbon atom furnishing the fluorophosphorane F4PCH2NMe2, which in turn attacks a second molecule of Me2NCH2F, abstracting a fluoride ion under the formation of the corresponding phosphate [F5PCH2NMe2] . Accordingly the amino function of the phosphate coordinates the remaining iminium ion forming the zwitterion 1 a. This reaction is analogous to the addition of trimethylamine (NMe3) to N,Ndimethylmethyleniminium chloride ([Me2NCH2] + Cl ), resulting in the formation of the ammonium salt [Me2NCH2NMe3] + Cl .[17] The reaction (Scheme 1) proceeds quickly at room temperature, therefore no intermediates were detected by NMR spec&

&

Chem. Eur. J. 2014, 20, 1 – 11

www.chemeurj.org

Figure 1. Structure of the compounds 1 a–1 d.

2


ÝÝ These are not the final page numbers!

Full Paper atom to the diastereotopic CF2 unit of the C2F5 substituent in a cis position to the aminoalkyl substituent results in a complex multiplet. The 31P NMR spectrum of [(C2F5)3F2P(CH2NMe2 CH2NMe2)] (1 d) exhibits a triplet of multiplets with a 1J(P,F) coupling constant of 826 Hz and therefore two chemically equivalent fluorine atoms, allowing a facial or meridional arrangement of the three C2F5 groups. The 19F NMR spectrum exhibits one set of signals for a C2F5 group trans to the CH2NMe2 CH2NMe2 unit and diastereotopic CF2 units of the two remaining chemically equivalent C2F5 groups. This is an indication for the existence of the facial arrangement of the three C2F5 groups. The solidstate structures of the synthesized phosphate derivatives with three pentafluoroethyl groups, which will be discussed later, express the facial geometry. In contrast to this, in the tris(pentafluoroethyl)trifluorophosphate ion a meridional arrangement of the pentafluoroethyl groups is favored over the facial structure as the minor product.[18] A dimethyl methylene iminium fragment was smoothly transferred onto PMe3 in acetonitrile to afford the phosphonium phosphate 2 a [Eq. (2)].

Figure 2. Molecular structure of [(C2F5)3F2PCH2NMe CH2PMe3] (4 d); 50 % probability amplitude displacement ellipsoids are shown; H atoms omitted for clarity. Selected bond lengths [pm] and angles [8]: P1 F1 163.69(10), P1 F2 166.05(10), P1 C1 199.1(2), P1 C7 189.0(2), N1 C7 147.9(2), N1 C8 147.0(2), N1 C9 146.2(2), P2 C9 181.6(2), P2 C10 177.8(2), F1-P1-C1 177.03(6), F2-P1-C4 172.53(6), C7-P1-C5 172.53(7), C7-N1-C8 108.62(12), C7-N1-C9 112.43(12), C8-N1-C9 110.38(13), C9-P2-C10 111.62(9), C9-P2-C11 107.25(8), C9-P2-C12 112.08(9), C10-P2-C11 108.68(11), C10-P2-C12 107.65(12).

compound 4 d crystallizes in the orthorhombic space group Pna21 (No. 33). The X-ray diffraction analysis (Figure 2) shows the picture of a zwitterionic phosphonium phosphate. The N C bonds N1 C7 (147.9(2) pm) and N1 C8 (147.0(2) pm) are slightly longer than N1 C9 (146.2(2) pm). Correspondingly the bond P2 C9 (181.6(2) pm) is slightly longer than the P C bonds to the methyl substituents (av. 178.4(2) pm). For comparison we investigated the reaction of tris(trifluoromethyl)phosphane (P(CF3)3) with fluoromethyldimethylamine. Oxidative addition of Me2NCH2F to P(CF3)3 yields [(CF3)3F2P(CH2NMe2 CH2NMe2)] as the main product (Scheme 3). In solution two conformers 5 and 5’ were observed by multinuclear NMR spectroscopy. In contrast to the pentafluoroethyl derivatives, it is possible to detect a second isomer 5’ with a fluorine atom in trans position to the alkylamino substituent. A single crystal suitable for X-ray diffraction analysis was grown from dichloromethane. Surprisingly the analysis did not show compound 5 or 5’, but instead the rearrangement product [(CF3)3F2P(CH2NMe CH2NMe3)] (6; Figure 3). Compound 6 evidently resulted from 5’ by a 1,3-trans-methylation. The N1 C6 distance of 141.3(1) pm is rather short, but still longer than the corresponding bond in the dimethylmethyleneiminium ion (126.3(5) pm as the bromide).[20] The N2 C6 (155.7(1) pm) distance is slightly longer than the N C bonds to the methyl groups. Compound 6 can be rationalized as the addition product of trimethylamine and an iminium ion bound to a phosphate backbone. A comparable situation is met in the cation of [Me2NCH2NMe3] + [TeF5] , which results from NMe3 and TeF2.[21] The phosphate moiety deviates from

This process mirrors the formation of the phosphonium salt [Me3PCH2NMe2] + Cl through aminoalkylation of PMe3 with [Me2NCH2] + Cl .[19] The phosphonium salts [Me3PCH2NMe2] + [(C2F5)nF5 nP(CH2NMe2)] (n = 1–3) were synthesized following the above-described synthetic protocol and fully characterized by NMR and IR spectroscopy and mass spectrometry. With an increasing number of perfluoroalkyl groups the obtained phosphates are less stable. When a solution of 1 d in dichloromethane was stirred at room temperature for 24 h the formation of the new product [(C2F5)3F2P(CH2NMe CH2NMe3)] (3 d) was observed (Scheme 2). The 1H NMR spectrum exhibits two signals for chemically inequivalent methyl groups with an integral ratio of one to three. Formally one methyl group shifted from the central to the terminal amino function resulting in the described integral ratio.

Scheme 2. Rearrangement of 1 d in dichloromethane and formation of 4 d.

Like the typical organotrimethyl ammonium salts compound 3 d transfers its organo group onto PMe3 with liberation of NMe3 and formation of [(C2F5)3F2P(CH2NMe CH2PMe3)] (4 d). Single crystals of 4 d were grown from dichloromethane. The Chem. Eur. J. 2014, 20, 1 – 11

www.chemeurj.org


3


&

&

Full Paper of decomposition, rendering it suitable for further transformations. However, this synthesis of a dialkylaminomethyl-substituted phosphate through oxidative addition of two equivalents of Me2NCH2F followed by hydrolysis is not efficient, because one equivalent of Me2NCH2F is lost during the process. Hence an alternative protocol is desirable. Among the alkali fluorides CsF is the most soluble in common organic solvents. Therefore, tris(pentafluoroethyl)phosphane, (P(C2F5)3), was stirred with CsF in acetonitrile at temperatures below 30 8C. NMR spectro-

Scheme 3. Reaction of P(CF3)3 with Me2NCH2F.

Scheme 4. Effective synthesis of the caesium salt of 7’ via the phosphoranide ion [P(C2F5)3F] .

scopic investigation of the reaction mixture showed the formation of a new species (Scheme 4). The observation of a 1J(P,F) coupling constant of 325 Hz indicates the addition of one fluoride ion to the phosphane forming the phosphoranide salt Cs + [P(C2F5)3F] . The 19F NMR spectrum further revealed two sets of signals for the axial and the equatorial pentafluoroethyl groups. The equatorial CF2 units exhibit diastereotopic fluorine atoms with a 2J(F,F) coupling constant of about 295 Hz. The corresponding tris(trifluoromethyl)fluorophosphoranide ion, [P(CF3)3F] , was synthesized by Rçschenthaler and Shyshkov.[22] The NMR data given for [NMe4] + [P(CF3)3F] are in good agreement with the obtained data for the phosphoranide ion [P(C2F5)3F] . The following reaction of the in situ generated Cs + [P(C2F5)3F] with one equivalent of Me2NCH2F affords the aminoalkyl-substituted phosphate Cs + [(C2F5)3F2P(CH2NMe2)] (7’). This reaction further underlines the proposed reaction mechanism for the reaction of an electron-poor phosphane with two equivalents of Me2NCH2F as depicted in Scheme 1. With the efficient synthesis of the caesium phosphate 7’, a basis for the further derivatization by means of salt elimination is established. Treatment of a solution of 7’ in acetonitrile with gaseous HCl leads to the precipitation of caesium chloride and the formation of the zwitterionic ammonium phosphate 8 a (Scheme 5). The resonance of the proton of the ammonium unit is observed at 6.9 ppm. Compound 8 a crystallizes in the triclinic space group P1¯ (No. 2). The molecular structure is shown in Figure 4. The N1 C7 distance, 151.4(2) pm, is slightly longer

Figure 3. Molecular structure of [(CF3)3F2PCH2NMe CH2NMe3] (6); 50 % probability amplitude displacement ellipsoids are shown. Selected bond lengths [pm] and angles [8]: P1 F1 166.21(6), P1 F2 164.78(6), P1 C4 191.4(1), P1 C1 195.3(1), N1 C4 146.3(1), N1 C6 141.4(1), N2 C6 155.7(1), N2 C8 149.8(1), F1-P1-C4 179.44(4), F2-P1-C2 179.27(4), C1-P1-C3 164.75(5), C4-N1-C5 116.54(8), C4-N1-C6 118.40(8), C5-N1-C6 115.39(8).

the octahedral symmetry along the C1-P1-C3 axis. Due to the steric demand of the alkylamino substituent the trifluoromethyl groups in cis position are pushed towards the fluorine atom F1 resulting in a C1-P1-C3 angle of 164.75(5)8. Iminium salts and their adducts with amines are, in general, sensitive towards hydrolysis. In keeping with this, the reaction of 1 d with aqueous sodium hydroxide affords the sodium salt of [(C2F5)3F2P(CH2NMe2)] (7), formaldehyde and dimethylamine [Eq. (3)]. The sodium salt of compound 7 is stable towards moisture and can be stored several months without any signs

&

&

Chem. Eur. J. 2014, 20, 1 – 11

www.chemeurj.org

4



Full Paper

Scheme 5. Alkylation of the caesium salt of [(C2F5)3F2P(CH2NMe2)] , 7’.

Figure 5. Molecular structure of [(C2F5)3F2P(CH2NMe2 CH2CHCH2)] (8 b); 50 % probability amplitude displacement ellipsoids are shown. Selected bond lengths [pm] and angles [8]: P1 F1 163.89(7), P1 F2 164.66(7), P1 C7 192.0(1), N1 C7 151.9(2), N1 C8 150.2(2), N1 C9 150.2(2), N1 C10 154.1(2), C11 C12 131.6(2), F1-P1-C1 177.70(5), F2-P1-C5 177.72(5), C3-P1-C7 170.35(5), C7-N1-C8 114.4(1), C7-N1-C9 111.5(1), C7-N1-C10 106.54(9), C8-N1-C9 109.1(1), C8-N1-C10 108.5(1), C9-N1-C10 106.43(9).

Figure 4. Molecular structure of [(C2F5)3F2P(CH2NMe2H)] (8 a); 50 % probability amplitude displacement ellipsoids are shown. Selected bond lengths [pm] and angles [8]: P1 F1 164.9(1), P1 F2 166.9(1), P1 C3 196.8(2), P1 C7 191.3(2), N1 C7 151.4(2), N1 C8 149.6(3), N1 C9 149.4(3), C7-N1-C8 112.2(2), C7-N1-C9 112.3(2), C8-N1-C9 109.8(2).

than the N C bonds to the methyl groups (149.4(3) and 149.6(3) pm). The angles between C7-N1-C8 (112.2(2)8) and C7-N1-C9 (112.3(2)8) are also slightly enlarged in comparison to C8-N1-C9 (109.8(2)8). The aminoalkylation of tertiary amines with organic halides is an efficient procedure for the generation of tetraorganylammonium salts. The high number of functionalized organic halides allows a wide variation. Alkylation of 7’ with allyl bromide leads to the precipitation of caesium bromide and the formation of the allyl ammonium derivative [(C2F5)3F2P(CH2NMe2 CH2CHCH2)] (8 b). In the 1H NMR spectrum, the CH2 group of the allyl substituent gives a multiplet at 4.0 ppm. After recrystallization from dichloromethane colorless crystals are obtained. The molecular structure of 8 b is shown in Figure 5. Bond lengths and angles within the phosphate moiety are comparable to the structures already described in this paper. The N C distances of the ammonium moiety (150.2(2)—154.1(2) pm) are in the range of a N C single bond. The C11 C12 distance of 131.6(2) pm is not unexceptional for a C C double bond. Another example for the successful aminoalkylation of [(C2F5)3F2P(CH2NMe2)] is the reaction with 4-chloromethylstyrene. After removal of the precipitated caesium chloride, 8 c can be isolated as a colorless solid in good yields. X-ray diffraction analysis confirmed the product formation. The molecular structure is shown in Figure 6. The bond lengths and angles of Chem. Eur. J. 2014, 20, 1 – 11

www.chemeurj.org


Figure 6. Molecular structure of [(C2F5)3F2P(CH2NMe2 CH2C6H4CHCH2)] (8 c); 50 % probability amplitude displacement ellipsoids are shown. Selected bond lengths [pm] and angles [8]: P1 F1 164.8(1), P1 F2 163.7(1), P1 C7 191.8(2), N1 C7 152.4(2), N1 C8 150.5(2), N1 C9 150.6(2), N1 C10 153.1(2), C7-N1-C8 112.9(2), C7-N1-C9 105.2(2), C7-N1-C10 110.9(1), C8-N1-C9 107.5(2), C8-N1-C10 111.1(2), C9-N1-C10 109.0(2).

both the phosphate and ammonium moiety are comparable to the allyl-substituted derivative 8 b.

Conclusions Fluoromethyldimethylamine is a versatile reactant for the synthesis of electron-deficient, functionalized phosphates. Thus, the oxidative addition of the reactant to (C2F5)nPF3 n (n = 1–3) selectively affords zwitterionic [(C2F5)nF5 nP(CH2NMe2 CH2NMe2)] (n = 1–3) in good yields. The course of the reaction involved the phosphoranide [P(C2F5)3F] , which was evidenced independently. The ammonium center in [(C2F5)nF5 nP(CH2NMe2 CH2NMe2)] (n = 1–3) was smoothly attacked by PMe3 to furnish phosphonium salts of the type [Me3PCH2NMe2] + [(C2F5)nF5 nP(CH2NMe2)] (n = 1–3). The zwitterion [(C2F5)3F2P(CH2NMe2 CH2NMe2)] proved to be thermolabile and suffers from a facile 1,3-methyl shift from the central ammonium function onto the terminal dimethylamino group. The highly nucleophilic PMe3 replaced trimethylamine from 5


&

&

Full Paper direct infusion with a syringe pump. Nitrogen served both as the nebulizer gas and the dry gas. Nitrogen was generated by a Bruker nitrogen generator NGM 11. Helium served as the cooling gas for the ion trap and collision gas for MS experiments. The spectra were recorded with Bruker Daltonik esquireNT 5.2 esquireControl software by the accumulation and averaging of several single spectra. Data analysis software 3.4 was used for processing the spectra. C, H, and N analyses were carried out with a HEKAtech Euro EA 3000. The crystal data for compounds 6 and 8 a were collected on a Bruker Nonius Kappa CCD diffractometer, for compounds 4 d, 8 b, and 8 c on a Super Nova (Dual, Cu at zero) Atlas diffractometer. Radiation used was MoKa radiation (l = 71.073 pm) for 4 d, 6, and 8 a, or CuKa radiation (l = 154.178 pm) for 8 b and 8 c. Suitable crystals were selected, coated with paratone oil and mounted onto the diffractometer. Using Olex2,[26] the structures were solved with the SHELXS[27] structure solution program using direct methods and refined with the SHELXL[27] refinement package using least-squares minimization. Details of the X-ray investigation are given in Table 2. CCDC-973110 (4), CCDC-973111 (6), CCDC-973112 (8 a), CCDC973113 (8 b), and CCDC-973114 (8 c) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

[(C2F5)3F2P(CH2NMe CH2NMe3)] yielding the corresponding phosphonium phosphate. Treatment of [(C2F5)3F2P(CH2NMe2 CH2NMe2)] with aqueous sodium hydroxide gave rise to the formation of the phosphate Na + [(C2F5)3F2P(CH2NMe2)] . An alternative and more economic approach to such alkali metal phosphates was based on the combination of the phosphane P(C2F5)3 with CsF prior to the reaction with Me2NCH2F. The nitrogen atom in this phosphate allows for protonation, alkylation, and arylation reactions. To the best of our knowledge the here synthesized compounds are the first examples of perfluoroalkylfluorophosphates with alkyl substituents bearing additional functional groups.

Experimental Section All chemicals were obtained from commercial sources and used without further purification. (C2F5)PF2,[23] (C2F5)2PF,[24] P(C2F5)3[25] and Me2NCH2F[14] were synthesized according to literature methods. Standard high vacuum techniques were employed throughout all preparative procedures. Nonvolatile compounds were handled in a dry N2 atmosphere using Schlenk techniques. The NMR spectra were recorded on a Bruker Model Avance III 300 spectrometer (31P 111.92 MHz; 19F 282.40 MHz; 13C 75.47 MHz, 1H 300.13 MHz) with positive shifts being downfield from the external standards (85 % orthophosphoric acid (31P), CCl3F (19F) and TMS (1H)). IR spectra were recorded on an ALPHA-FT-IR spectrometer (Bruker). ESI mass spectra were recorded using an Esquire 3000 ion-trap mass spectrometer (Bruker Daltonik GmbH, Bremen, Germany) equipped with a standard ESI/APCI source. Samples were introduced by

Synthesis of [F5P(CH2NMe2CH2NMe2)] (1 a): Me2NCH2F (0.39 g, 5.00 mmol) was condensed into a solution of PF3 (0.22 g, 2.50 mmol) in diethyl ether (50 mL) at 196 8C and slowly warmed to room temperature. The white precipitate was filtered off, washed with diethyl ether, and dried in vacuo yielding 1 a (0.60 g, 2.48 mmol, 99 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 2.6 (s, 6 H; CH3), 2.9 (s, 6 H; CH3), 3.0 (d/quint, 2J(P,H) = 17 Hz, 3 J(F,H) = 6 Hz, 2 H; PCH2N), 4.0 ppm (s, 2 H; NCH2N); 1H{31P} NMR

Table 2. Crystal data and refinement characteristics for compounds 4 d, 6, 8 a, 8 b, and 8 c.

formula a [pm] b [pm] c [pm] a [8] b [8] g [8] V [106 pm3] Z 1calcd [g cm 3] crystal system space group shape/color crystal size [mm3] T [K] q range [8] index range

total data collected unique data observed data (I > 2s) m [mm 1] R1/wR2 [I > 2s(I)] R1/wR2 (all data) goodness of fit (Sall) R(int)/R(s) D1max/min [106 e pm 3] F(000)

&

&

Chem. Eur. J. 2014, 20, 1 – 11

4d

6

8a

8b

8c

C12H16F17NP2 1365.63(1) 1016.98(1) 1430.06(1) 90 90 90 1986.10(3) 4 1.870 orthorhombic Pna21 (no. 33) colorless 0.38 0.19 0.04 100.0(1)) 2.85–30.09 19 h 19 14 k 14 20 l 20 110 587 5833 5668 0.375 0.0194/0.0483 0.0208/0.0493 1.121 0.0340 0.31/ 0.19 1112.0

C9H16F11N2P 772.42(2) 1433.13(3) 1372.57(4) 90 100.497(1) 90 1493.98(7) 4 1.744 monoclinic P21/c (no. 14) colorless 0.30 0.27 0.16 100(2) 3.04–30.00 10 h 10 20 k 18 19 l 19 27 020 4341 3764 0.302 0.0267/0.0702 0.0327/0.0729 1.033 0.028 0.455/ 0.300 792

C9H9F17NP 852.23(3) 912.33(3) 1023.87(3) 90.090(2) 99.280(2) 102.587(2) 766.22(4) 2 2.103 triclinic P1¯ (no. 2) colorless 0.30 0.17 0.03 100(2) 3.73–27.50 11 h 11 11 k 11 13 l 13 23 076 3505 2796 0.369 0.0358/0.0832 0.0508/0.0912 1.037 0.057 0.408/ 0.394 476

C12H13F17NP 1355.99(2) 933.25(1) 1440.65(2) 90 101.430(1) 90 1786.94(4) 4 1.952 monoclinic P21/n (no. 14) colorless 0.29 0.24 0.11 100 4.09–72.60 16 h 16 11 k 11 17 l 17 44 258 3511 3482 3.046 0.0238/0.0602 0.0240/0.0603 1.097 0.0285 0.37/ 0.28 1040.0

C18H17F17NP 1122.63(4) 1339.89(8) 1566.11(5) 108.402(5) 90.061(3) 98.626(4) 2207.1(2) 4 1.810 triclinic P1¯ (no. 2) colorless 0.30 0.18 0.05 100.0(1) 3.82–72.58 13 h 13 16 k 16 19 l 19 122 592 15 812 14 055 2.564 0.0547/0.1512 0.0608/0.1604 1.039 0.048 0.68/ 0.51 1200.0

www.chemeurj.org

6



Full Paper Synthesis of [Me3PCH2NMe2] + [(C2F5)F4P(CH2NMe2)] (2 b): PMe3 (0.23 g, 3.00 mmol) was condensed into a solution of 1 b (0.83 g, 2.43 mmol) in acetonitrile (10 mL) and stirred at room temperature for 1 h. Removal of all volatile compounds yielded 2 b (1.02 g, 2.43 mmol, 100 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 1.8 (d, 2J(P,H) = 14 Hz, 9 H; PCH3), 2.3 (d, 4J(P,H) = 1 Hz, 6 H; [Me3PCH2N(CH3)2] + ), 2.4 (s, 6 H; [(C2F5)F4PCH2N(CH3)2] ), 2.5 (pseudo-sept, 2J(P,H)/3J(F,H) = 7 Hz, 2 H; [(C2F5)F4PCH2NMe2] ), 3.2 ppm (d, 2J(P,H) = 5 Hz, 2 H; [Me3PCH2NMe2] + ); 1H{31P} NMR ([D3]acetonitrile, RT): d = 1.8 (s, 9 H; P-CH3), 2.3 (s, 6 H; [Me3PCH2N(CH3)2] + ), 2.4 (s, 6 H; [(C2F5)F4PCH2N(CH3)2] ), 2.5 (quint, 3J(F,H) = 7 Hz, 2 H; [(C2F5)F4PCH2NMe2] ), 3.3 ppm (s, 2 H; [Me3PCH2NMe2] + ); 13 1 C{ H} NMR ([D3]acetonitrile, RT): d = 5.9 (d, 1J(P,C) = 54 Hz, [(CH3)3PCH2NMe2] + ), 46.3 (d/quint, 3J(P,C) = 13 Hz, 4J(F,C) = 2 Hz, [(C2F5)F4PCH2N(CH3)2] ), 47.2 (d, 3J(P,C) = 8 Hz, [Me3PCH2N(CH3)2] + ), 52.5 (d, 1J(P,C) = 72 Hz, [Me3PCH2NMe2] + ), 66.2 ppm (d/quint, 1 J(P,C) = 271 Hz, 2J(F,C) = 45 Hz, [(C2F5)F4PCH2NMe2] ); 13C{19F} NMR ([D3]acetonitrile, RT): d = 118.4 (d, 1J(P,C) = 332 Hz, CF2), 121.1 ppm (d/m, 2J(P,C) = 30 Hz, CF3); 19F NMR ([D3]acetonitrile, RT): d = 117.4 (d/quint, 2J(P,F) = 102 Hz, 3J(F,F) = 10 Hz, 2 F; CF2), 82.7 (m, 3 F; 58.6 ppm (d/m, 1J(P,F) = 932 Hz, 4 F; PF4); 31P NMR CF3), ([D3]acetonitrile, RT): d = 134.6 (quint/t/t/quart, 1J(P,F) = 933 Hz, 2 J(P,F) = 102 Hz, 2J(P,H) = 14 Hz, 3J(P,F) = 2 Hz, [(C2F5)F4PCH2NMe2] ), 25.3 ppm (m, [Me3PCH2NMe2] + ); 31P{1H} NMR ([D3]acetonitrile, RT): d = 134.6 (quint/t/quart, 1J(P,F) = 933 Hz, 2J(P,F) = 102 Hz, 3J(P,F) = 2 Hz, [(C2F5)F4PCH2NMe2] ), 25.3 ppm (s, [Me3PCH2NMe2] + ); IR (solid): n˜ = 414 (w), 434 (w), 492 (w), 531 (m), 581 (s), 599 (m), 622 (s), 637 (m), 731 (s), 790 (m), 837 (m), 886 (w), 901 (w), 969 (m), 1043 (m), 1084 (m), 1137 (m), 1179 (m), 1201 (m), 1303 (w), 1325 (w), 1434 (w), 1459 (w), 2788 (w), 2819 (w), 2960 cm 1 (w); MS (ESI): m/z (%): 284 (100) [(C2F5)F4PCH2NMe2] , 134 (100) [Me3PCH2NMe2] + .

([D3]acetonitrile, RT): d = 2.6 (s, 6 H; CH3), 2.9 (s, 6 H; CH3), 3.0 (quint, 3 J(F,H) = 6 Hz, 2 H; PCH2N), 4.0 ppm (s, 2 H; NCH2N); 13C{1H} NMR ([D3]acetonitrile, RT): d = 44.5 (s, CH3), 46.6 (s, CH3), 65.9 (d/quint, 1 J(P,C) = 264 Hz, 2J(F,C) = 54 Hz, PCH2N), 91.2 ppm (s, NCH2N); 19 F NMR ([D3]acetonitrile, RT): d = 67.3 (d/quint, 1J(P,F) = 722 Hz, 2 J(F,F) = 41 Hz, 1 F; PF), 53.9 ppm (d, 1J(P,F) = 821 Hz, 4 F; PF4); 31 P NMR ([D3]acetonitrile, RT): d = 139.9 ppm (quint/d/t, 1J(P,F) = 823 Hz, 1J(P,F) = 721 Hz, 2J(P,H) = 17 Hz, P); IR (solid): n˜ = 519 (m), 553 (m), 570 (s), 618 (m), 709 (m), 771 (s), 855 (m), 919 (w), 1080 (m), 1366 (w), 1459 (w), 1489 (w), 2806 (w), 2856 (w), 3252 cm 1 (w); MS (ESI): m/z (%): 184 (100) [F5PCH2NMe2] ; elemental analysis calcd (%) for C6H16F5N2P: C 29.74, H 6.66, N 11.57; found: C 28.11, H 6.51, N 10.61. Synthesis of [Me3PCH2NMe2] + [F5P(CH2NMe2)] (2 a): PMe3 (0.06 g, 0.83 mmol) was condensed into a solution of 1 a (0.14 g, 0.56 mmol) in acetonitrile (4 mL) and stirred at room temperature for 1 h. All volatile compounds were removed in vacuo yielding 2 a (0.17 g, 0.53 mmol, 95 %) as colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 1.8 (d, 2J(P,H) = 14 Hz, 9 H; PCH3), 2.3 (d, 4J(P,H) = 2 Hz, 6 H; [Me3PCH2N(CH3)2] + ), 2.4 (s, 6 H; [F5PCH2N(CH3)2] ), 2.4 (pseudo-sept, 2 J(P,H)/3J(F,H) = 7 Hz, 2 H; [F5P-CH2-NMe2] ), 3.3 ppm (d, 2J(P,H) = 5 Hz, 2 H; [Me3PCH2NMe2] + ); 1H{31P} NMR ([D3]acetonitrile, RT): d = 1.8 (s, 9 H; P-CH3), 2.3 (s, 6 H; [Me3PCH2N(CH3)2] + ), 2.4 (s, 6 H; [F5PCH2N(CH3)2] ), 2.4 (quint, 3J(F,H) = 7 Hz, 2 H; [F5PCH2NMe2] ), 3.3 ppm (s, 2 H; [Me3PCH2NMe2] + ); 13C{1H} NMR ([D3]acetonitrile, RT): d = 5.9 (d, 1J(P,C) = 54 Hz, [(CH3)3PCH2NMe2] + ), 46.3 (d/m, 3 J(P,C) = 13 Hz, [F5PCH2N(CH3)2] ), 47.2 (d, 3J(P,C) = 7 Hz, [Me3PCH2N(CH3)2] + ), 52.4 (d, 1J(P,C) = 72 Hz, [Me3PCH2NMe2] + ), 66.5 ppm (d/ quint, 1J(P,C) = 278 Hz, 2J(F,C) = 48 Hz, [F5PCH2NMe2] ); 19F NMR ([D3]acetonitrile, RT): d = 59.9 (d/quint, 1J(P,F) = 685 Hz, 2J(F,F) = 37 Hz, 1 F; PF), 56.2 ppm (d/d/t, 1J(P,F) = 867 Hz, 2J(F,F) = 36 Hz, 3 J(F,H) = 7 Hz, 4 F; PF4); 31P NMR ([D3]acetonitrile, RT): d = 130.6 (quint/d/t/m, 1J(P,F) = 868 Hz, 1J(P,F) = 684 Hz, 2J(P,H) = 14 Hz, [F5PCH2NMe2] ), 25.5 ppm (m, [Me3PCH2NMe2] + ); IR (solid): n˜ = 518 (m), 543 (w), 592 (s), 697 (s), 748 (s), 807 (m), 859 (m), 891 (w), 906 (w), 969 (m), 987 (m), 1042 (m), 1263 (w), 1282 (w), 1298 (w), 1429 (w), 1454 (w), 1467 (w), 2765 (m), 2814 (w), 2841 (w), 2942 (w), 3000 cm 1 (w); MS (ESI): m/z (%): 184 (100) [F5PCH2NMe2] , 134 (100) [Me3PCH2NMe2] + .

Synthesis of [(C2F5)2F3P(CH2NMe2 CH2NMe2)] (1 c): Me2NCH2F (0.17 g, 2.22 mmol) was condensed into a solution of (C2F5)2PF (0.32 g, 1.11 mmol) in diethyl ether (10 mL) at 196 8C and slowly warmed to room temperature. The white precipitate was filtered off, washed with diethyl ether, and dried in vacuo yielding 1 c (0.38 g, 0.86 mmol, 77 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 2.7 (s, 6 H; CH3), 2.9 (s, 6 H; CH3), 3.1 (m, 2 H; PCH2N), 4.3 ppm (s, 2 H; NCH2N); 1H{31P} NMR ([D3]acetonitrile, RT): d = 2.7 (s, 6 H; CH3), 2.9 (s, 6 H; CH3), 3.1 (m, 2 H; PCH2N), 4.3 ppm (s, 2 H; NCH2N); 13C{1H} NMR ([D3]acetonitrile, RT): d = 44.4 (s, CH3), 46.8 (m, CH3), 65.4 (d/m, 1J(P,C) = 199 Hz, PCH2N), 92.5 ppm (s, NCH2N); 13C{19F} NMR ([D3]acetonitrile, RT): 120.3 (d, 2J(P,C) = 20 Hz, CF3), 120.6 ppm (d, 2J(P,C) = 26 Hz, CF3); 19F NMR ([D3]acetonitrile, RT): d = 117.7 (m, 2 F; CF2), 116.4 (m, 2 F; CF2), 82.6 (m, 3 F; CF3), 81.7 (m, 3 F; CF3), 77.1 (br d, 1J(P,F) = 857 Hz, 30.7 ppm (br d, 1J(P,F) = 887 Hz, 1 F; PF); 31P NMR 2 F; PF2), ([D3]acetonitrile, RT): d = 146.3 ppm (d/t/m, 1J(P,F) = 889 Hz, 1 J(P,F) = 860 Hz, P); IR (solid): n˜ = 426 (m), 505 (w), 537 (w), 573 (m), 618 (s), 708 (s), 754 (s), 833 (w), 855 (w), 878 (m), 968 (m), 1066 (m), 1103 (m), 1125 (s), 1171 (s), 1203 (s), 1311 (m), 1459 (w), 1483 (w), 2811 (w), 2956 cm 1 (w); MS (ESI): m/z (%): 384 (100) [(C2F5)2F3PCH2NMe2] .

Synthesis of [(C2F5)F4P(CH2NMe2 CH2NMe2)] (1 b): Me2NCH2F (0.56 g, 7.33 mmol) was condensed into a solution of (C2F5)PF2 (0.69 g, 3.69 mmol) in diethyl ether (50 mL) at 196 8C and slowly warmed to room temperature. The white precipitate was filtered off, washed with diethyl ether, and dried in vacuo yielding 1 b (1.16 g, 3.39 mmol, 92 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 2.6 (s, 6 H; CH3), 2.9 (s, 6 H; CH3), 3.0 (d/ quint, 2J(P,H) = 18 Hz, 3J(F,H) = 6 Hz, 2 H; PCH2N), 4.1 ppm (s, 2 H; NCH2N); 1H{31P} NMR ([D3]acetonitrile, RT): d = 2.6 (s, 6 H; CH3), 2.9 (s, 6 H; CH3), 3.0 (quint, 3J(F,H) = 6 Hz, 2 H; PCH2N), 4.1 ppm (s, 2 H; NCH2N); 13C{1H} NMR ([D3]acetonitrile, RT): d = 44.6 (s, CH3), 46.8 (s, CH3), 65.5 (d/quint, 1J(P,C) = 260 Hz, 2J(F,C) = 51 Hz, PCH2N), 91.8 ppm (s, NCH2N); 13C{19F} NMR ([D3]acetonitrile, RT): 117.2 (d/m, 1 J(P,C) = 330 Hz, CF2), 120.6 ppm (d, 2J(P,C) = 30 Hz, CF3); 19F NMR ([D3]acetonitrile, RT): d = 118.7 (d/quint, 2J(P,F) = 104 Hz, 3J(F,F) = 10 Hz, 2 F; CF2), 83.2 (m, 3 F; CF3), 55.2 ppm (d, 1J(P,F) = 908 Hz, 4 F; PF4); 31P NMR ([D3]acetonitrile, RT): d = 140.9 ppm (quint/t/t, 1 J(P,F) = 908 Hz, 2J(P,F) = 104 Hz, 2J(P,H) = 18 Hz, P); 31P{1H} NMR ([D3]acetonitrile, RT): d = 140.9 ppm (quint/t, 1J(P,F) = 907 Hz, 2 J(P,F) = 103 Hz, P); IR (solid): n˜ = 414 (w), 439 (w), 532 (m), 566 (m), 594 (m), 630 (m), 642 (m), 719 (m), 734 (m), 752 (s), 879 (m), 898 (w), 983 (m), 1092 (m), 1142 (m), 1192 (m), 1325 (m), 3234 cm 1 (w); MS (ESI): m/z (%): 284 (84) [(C2F5)F4PCH2NMe2] . Chem. Eur. J. 2014, 20, 1 – 11

www.chemeurj.org


Synthesis of [Me3PCH2NMe2] + [(C2F5)2F3P(CH2NMe2)] (2 c): PMe3 (0.05 g, 0.68 mmol) was condensed into a solution of 1 c (0.24 g, 0.54 mmol) in dichloromethane (10 mL) and stirred at room temperature for 12 h. All volatile compounds were removed in vacuo yielding 2 c (0.26 g, 0.50 mmol, 93 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 1.8 (d, 2J(P,H) = 14 Hz, 9 H; PCH3), 2.4 (s, 6 H; [Me3PCH2N(CH3)2] + ), 2.6 (s, 6 H; [(C2F5)2F3PCH2N(CH3)2] ), 2.9 (m, 2 H; [(C2F5)2F3PCH2NMe2] ), 3.3 ppm (d, 2J(P,H) = 6 Hz, 2 H; [Me3PCH2NMe2] + ); 1H{31P} NMR ([D3]acetonitrile, RT): d = 1.8 (s, 9 H;

7


&

&

Full Paper [Me3PCH2NMe2] + ); 31P{1H} NMR ([D3]acetonitrile, RT): d = 150.2 (t/ 1 J(P,F) = 859 Hz, [(C2F5)3F2PCH2NMe2] ), 25.3 ppm (s, m, [Me3PCH2NMe2] + ); IR (solid): n˜ = 399 (m), 430 (m), 484 (m), 533 (m), 554 (m), 562 (m), 596 (m), 616 (s), 657 (s), 678 (s), 719 (m), 742 (m), 779 (w), 826 (w), 849 (m), 882 (m), 911 (w), 937 (s), 962 (m), 974 (m), 1036 (m), 1076 (m), 1097 (m), 1127 (s), 1162 (s), 1184 (s), 1207 (s), 1283 (m), 1302 (m), 1422 (w), 1447 (w), 1469 (w), 2764 (w), 2790 (w), 2824 (w), 2839 (w), 2900 (w), 2962 (w), 2995 cm 1 (w); MS (ESI): m/z (%): 484 (100) [(C2F5)3F2PCH2NMe2] , 134 (100) [Me3PCH2NMe2] + .

P-CH3), 2.4 (s, 6 H; [Me3PCH2N(CH3)2] + ), 2.6 (s, 6 H; [(C2F5)F4PCH2N(CH3)2] ), 2.9 (m, 2 H; [(C2F5)2F3PCH2NMe2] ), 3.3 ppm (s, 2 H; [Me3PCH2NMe2] + ); 13C{1H} NMR ([D3]acetonitrile, RT): d = 6.1 (d, 1 J(P,C) = 54 Hz, [(CH3)3PCH2NMe2] + ), 46.2 (d/m, 3J(P,C) = 9 Hz, [(C2F5)2F3PCH2N(CH3)2] ), 47.2 (d, 3J(P,C) = 7 Hz, [Me3PCH2N(CH3)2] + ), 52.6 (d, 1J(P,C) = 71 Hz, [Me3PCH2NMe2] + ), 65.2 ppm (d/m, 1J(P,C) = 206 Hz, [(C2F5)2F3PCH2NMe2] ); 13C{19F} NMR ([D3]acetonitrile, RT): d = 120.5 (d, 2J(P,C) = 15 Hz, CF3), 120.8 ppm (d, 2J(P,C) = 23 Hz, CF3); 19 F NMR ([D3]acetonitrile, RT): d = 118.6 (d/m, 2J(P,F) = 65 Hz, 2 F; a C F2CbF3), 116.3 (d/m, 2 F; 2J(P;F) = 101 Hz, CcF2CdF3), 82.4 (m, 3 F; CaF2CbF3), 81.7 (m, 3 F; CcF2CdF3), 80.6 (d/d/m, 1J(P,F) = 860 Hz, 2J(F,F) = 35 Hz, 2 F; PF2), 35.1 ppm (d/m, 1J(P,F) = 892 Hz, 1 F; PF); 31P NMR ([D3]acetonitrile, RT): d = 144.5 (d/t/m, 1J(P,F) = 901 Hz, 1J(P,F) = 865 Hz, [(C2F5)2F3PCH2NMe2] ), 25.4 ppm (m, [Me3PCH2NMe2] + ); 31P{1H} NMR ([D3]acetonitrile, RT): d = 144.5 (d/ 1 1 J(P,F) = 901 Hz, J(P,F) = 865 Hz, [(C2F5)2F3PCH2NMe2] ), t/m, 25.4 ppm (s, [Me3PCH2NMe2] + ); IR (solid): n˜ = 422 (w), 482 (w), 533 (m), 561 (m), 579 (m), 599 (s), 634 (m), 681 (m), 727 (s), 748 (s), 772 (m), 855 (m), 884 (w), 917 (w), 962 (s), 1043 (m), 1081 (m), 1122 (s), 1172 (s), 1203 (s), 1304 (m), 1426 (w), 1457 (w), 1469 (w), 1689 (w), 2728 (w), 2770 (w), 2792 (w), 2818 (w), 2845 (w), 2887 (w), 2941 (w), 2959 cm 1 (w); MS (ESI): m/z (%): 384 (34) [(C2F5)2F3PCH2NMe2] , 134 (84) [Me3PCH2NMe2] + .

Synthesis of [(C2F5)3F2PCH2NMe CH2NMe3] (3 d): Me2NCH2F (0.34 g, 4.44 mmol) was condensed into a solution of P(C2F5)3 (0.90 g, 2.31 mmol) in dichloromethane (7 mL) at 196 8C and slowly warmed to room temperature. The reaction mixture was stirred overnight. All volatile compounds were removed in vacuo yielding 3 d (1.20 g, 2.21 mmol, 96 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 2.8 (s, 9 H; [(C2F5)3F2PCH2NMe-CH2N(CH3)3]), 2.9 (m, 3 H; [(C2F5)3F2PCH2N(CH3)-CH2N(CH3)3]), 3.4 (m, 2 H; PCH2N), 4.5 ppm (br s, 2 H; NCH2N); 13C{1H} NMR ([D3]acetonitrile, RT): d = 43.6 (s, N(CH3)), 48.3 (s, N(CH3)3), 60.6 (d/m, 1J(P,C) = 160 Hz, PCH2N), 94.6 ppm (s, NCH2N); 19F NMR ([D3]acetonitrile, RT): d = 111.8 (br m, 2 F; CF2), 111.1/ 108.7 (br m, 4 F; CF2), 81.3 (t, J = 18 Hz, 3 F; CF3), 80.5 (br s, 6 F; CF3), 47.0 ppm (d, 1J(P,F) = 866 Hz, 2 F; PF2); 31P NMR ([D3]acetonitrile, RT): d = 147.2 ppm (t/m, 1J(P,F) = 870 Hz, P); IR (solid): n˜ = 425 (m), 433 (m), 469 (w), 485 (w), 516 (m), 572 (m), 592 (m), 615 (s), 631 (m), 661 (s), 691 (s), 743 (m), 796 (m), 847 (m), 873 (w), 937 (s), 985 (w) 1066 (s), 1082 (s), 1134 (s), 1170 (s), 1207 (s), 1283 (s), 1359 (w), 1394 (w), 1418 (w), 1430 (w), 1476 (w), 1490 (w), 2967 cm 1 (w); MS (ESI): m/z (%): 469 (33) [(C2F5)3F2PCH2NMeH] .

Synthesis of [(C2F5)3F2P(CH2NMe2 CH2NMe2)] (1 d): Me2NCH2F (0.92 g, 11.92 mmol) was condensed into a solution of P(C2F5)3 (2.33 g, 6.00 mmol) in diethyl ether (50 mL) at 196 8C and slowly warmed to room temperature. The white precipitate was filtered off, washed with diethyl ether, and dried in vacuo yielding 1 d (3.01 g, 05.55 mmol, 93 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 2.7 (s, 6 H; CH3), 2.8 (s, 6 H; CH3), 3.3 (m, 2 H; PCH2N), 4.2 ppm (s, 2 H; NCH2N); 13C{1H} NMR ([D3]acetonitrile, RT): d = 44.5 (s, CH3), 46.9 (m, CH3), 64.2 (d/m, 1J(P,C) = 156 Hz, PCH2N), 94.9 ppm (s, NCH2N); 13C{19F} NMR ([D3]acetonitrile, RT): 120.5 (d, 2J(P,C) = 15 Hz, CF3), 120.7 ppm (d, 2J(P,C) = 24 Hz, CF3); 19 F NMR ([D3]acetonitrile, RT): d = 112.0 (m, 2 F; CF2), 111.4/ 108.5 (m, 4 F; CF2), 85.5 (m, 3 F; CF3), 80.7 (m, 6 F; CF3), 41.5 ppm (d, 1J(P,F) = 826 Hz, 2 F; PF2); 31P NMR ([D3]acetonitrile, RT): d = 155.0 ppm (t/m, 1J(P,F) = 826 Hz, P); IR (solid): n˜ = 401 (m), 425 (m), 439 (w), 471 (w), 529 (m), 567 (m), 611 (s), 633 (m), 662 (s), 680 (s), 703 (s), 746 (w), 788 (w), 833 (w), 853 (m), 875 (w), 949 (s), 993 (w), 1055 (m), 1084 (s), 1104 (m), 1134 (s), 1169 (s), 1206 (s), 1283 (m), 1406 (w), 1429 (w), 1468 (w), 1480 (w), 1490 cm 1 (w); MS (ESI): m/z (%): 484 (62) [(C2F5)3F2P(CH2NMe2)] .

Synthesis of [(C2F5)3F2PCH2NMe CH2PMe3] (4 d): Me2NCH2F (0.33 g, 4.32 mmol) was condensed into a solution of P(C2F5)3 (0.87 g, 2.24 mmol) in dichloromethane (7 mL) at 196 8C, slowly warmed to room temperature and stirred overnight. All volatile compounds were removed in vacuo. The residue was solved in acetonitrile and filtered under inert conditions prior to the addition of PMe3 (0.17 g, 2.19 mmol). The reaction mixture was stirred overnight. Removal of the solvent yielded 4 d (1.01 g, 1.81 mmol, 84 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 1.8 (d, 2 J(P,H) = 14 Hz, 9 H; P(CH3)3), 2.5 (d, 4J(P,H) = 3 Hz, 3 H; N(CH3)), 3.1 (br m, 2 H; (C2F5)3F2PCH2N), 3.5 ppm (t, 2/4J(P,H) = 2 Hz, 2 H; NCH2PMe3); 13C{1H} NMR ([D3]acetonitrile, RT): d = 7.0 (d, 1J(P,C) = 53 Hz, P(CH3)3), 45.9 (d/t, 3J(P,C) = 11 Hz, J = 3 Hz, N(CH3)), 53.2 (d, quart, 1J(P,C) = 68 Hz, J = 3 Hz, NCH2P(CH3)3), 65.0 (d/m, 1J(P,C) = 171 Hz, (C2F5)3F2PCH2N); 13C{19F} NMR ([D3]acetonitrile, RT): 120.8 (d, 2 J(P,C) = 13 Hz. CF3), 121.1 ppm (d, 2J(P,C) = 26 Hz, CF3); 19F NMR ([D3]acetonitrile, RT): d = 111.4 (m, 2 F; CF2), 111.5/ 109.0 (m, 4 F; CF2), 81.2 (t, J = 18 Hz, 3 F; CF3), 80.7 (br m, 6 F; CF3), 45.3 ppm (d, 1J(P,F) = 862 Hz, 2 F; PF2); 31P NMR ([D3]acetonitrile, RT): d = 148.6 ppm (t/m, 1J(P,F) = 861 Hz, (C2F5)3F2P), 25.2 ppm (m, PMe3); IR (solid): n˜ = 396 (w), 429 (w), 467 (w), 488 (w), 530 (s), 552 (s), 592 (w), 616 (m), 628 (m), 467 (s), 656 (s), 688 (s), 716 (m), 745 (w), 858 (w), 887 (m), 915 (w), 942 (s), 960 (m), 977 (m), 1043 (w), 1069 (s), 1079 (s), 1103 (m), 1132 (s), 1167 (s), 1210 (s), 1283 (s), 1306 (w), 1421 (w), 1457 (w), 1471 (w), 1671 (w), 2800 (w), 2934 (w), 2966 (w), 3015 cm 1 (w); MS (ESI): m/z (%): 540 (100) [M F] + .

Synthesis of [Me3PCH2NMe2] + [(C2F5)3F2P(CH2NMe2)] (2 d): PMe3 (0.13 g, 1.72 mmol) was condensed into a solution of 1 d (0.91 g, 1.68 mmol) in acetonitrile (10 mL) and stirred at room temperature for 12 h. All volatile compounds were removed in vacuo yielding 2 d (0.95 g, 1.54 mmol, 92 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 1.8 (d, 2J(P,H) = 14 Hz, 9 H; PCH3), 2.3 (s, 6 H; [Me3PCH2N(CH3)2] + ), 2.4 (s, 6 H; [(C2F5)3F2PCH2N(CH3)2] ), 2.8 (m, 2 H; [(C2F5)3F2PCH2NMe2] ), 3.2 ppm (d, 2J(P,H) = 5 Hz, 2 H; [Me3PCH2NMe2] + ); 13C{1H} NMR ([D3]acetonitrile, RT): d = 6.0 (d, 1 J(P,C) = 54 Hz, [(CH3)3PCH2NMe2] + ), 46.9 (d/t, 3J(P,C) = 12 Hz, 4 J(F,C) = 3 Hz, [(C2F5)3F2PCH2N(CH3)2] ), 47.1 (d, 3J(P,C) = 8 Hz, [Me3PCH2N(CH3)2] + ), 52.6 (d, 1J(P,C) = 74 Hz, [Me3PCH2NMe2] + ), 1 2 J(P,C) = 176 Hz, J(F,C) = 36 Hz, 65.2 ppm (d/t/m, 13 19 [(C2F5)3F2PCH2NMe2] ); C{ F} NMR ([D3]acetonitrile, RT): d = 120.9 (d, 2J(P,C) = 13 Hz, CcF2CdF3), 121.2 ppm (d, 2J(P,C) = 25 Hz, CaF2CbF3); 19 F NMR ([D3]acetonitrile, RT): d = 111.8/ 109.1 (m, 2J(F,F) = 320 Hz, 4 F; CcF2CdF3), 111.4 (m, 2 F; CaF2CbF3), 81.1 (t, J = 18 Hz, 3 F; CaF2CbF3), 80.0 (m, 6 F; CcF2CdF3), 46.7 ppm (d, 1J(P,F) = 861 Hz, 2 F; PF2); 31P NMR ([D3]acetonitrile, RT): d = 150.2 (t/m, 1 J(P,F) = 859 Hz, [(C2F5)3F2PCH2NMe2] ), 25.3 ppm (m,

&

&

Chem. Eur. J. 2014, 20, 1 – 11

www.chemeurj.org

Synthesis of Cs + [(C2F5)3F2PCH2NMe2] (7’): CsF (0.54 g, 3.55 mmol) was suspended in acetonitrile (10 mL) and cooled to 78 8C prior to the addition of P(C2F5)3 (0.97 g, 2.50 mmol). The reaction mixture was slowly warmed to 30 8C and investigated by NMR spectroscopy. 19F NMR (acetonitrile, RT): d = 111.0 (br d, 2J(P,F) = 135 Hz, 2 F; CF2), 109.1 (br d, 2J(F,F) = 296 Hz, 2 F; CFAFB), 106.4 (d/m, 2 J(F,F) = 295 Hz, 2 F; CFAFB), 80.8 (m, 6 F; CF3), 78.0 (m, 3 F; CF3),

8



Full Paper 21.0 ppm (d/m, 1J(P,F) = 325 Hz, 1 F; PF); RT): d = 33.9 ppm (d/m, 1J(P,F) = 325 Hz, P).

31

pseudo-quint, 1J(P,F) = 824 Hz, 2J(P,F) = 95 Hz, 2J(P,F) = 52 Hz, P); IR (solid): n˜ = 417 (w), 431 (w), 467 (w), 498 (w), 537 (m), 565 (s), 596 (m), 620 (m), 643 (s), 671 (s), 697 (s), 711 (s), 747 (m), 792 (w), 849 (m), 872 (w), 912 (w), 947 (s), 971 (s), 998 (m), 1011 (m), 1071 (s), 1090 (s), 1117 (m), 1140 (s), 1160 (s), 1175 (s), 1188 (s), 1210 (s), 1238 (m), 1274 (m), 1375 (w), 1426 (w), 1480 (w), 1648 (w), 1674 (w), 1703 cm 1 (w); MS (ESI): m/z (%): 548 (28) [M + Na] + , 506 (65) [M F] + , 406 (100) [M C2F5] + , 268 (89) [M F 2(C2F5)] + . Synthesis of [(C2F5)3F2PCH2NMe2 CH2C6H4CHCH2] (8 c): Compound 7’ (1.13 g, 1.83 mmol) was dissolved in acetonitrile (10 mL) prior to the addition of 4-chloromethylstyrene (0.50 g, 3.29 mmol). The reaction mixture was stirred at room temperature for 12 h until the precipitation of CsCl was completed. The reaction mixture was filtered under inert conditions and washed with acetonitrile. Removal of the solvent and recrystallization from dichloromethane yielded 8 c (0.62 g, 1.01 mmol, 55 %) as colorless crystals. 1H NMR ([D3]acetonitrile, RT): d = 3.1 ppm (s, 6 H; N(CH3)2), 3.7 (m, 2 H; PCH2N), 4.5 (d, 4J(P,H) = 3 Hz, 2 H; NCH2C), 5.4 (d/m, 3J(H,H) = 11 Hz (Z), 1 H; CHCHZH), 5.9 (d/m, 3J(H,H) = 17 Hz (E), 1 H; CHCHHE), 6.8 (d/d, 3J(H,H) = 17 Hz (E), 3J(H,H) = 11 Hz (Z), 1 H; CHCH2), 7.5 (m, 2 H; ortho-H), 7.6 ppm (m, 2 H; meta-H); 13C{1H} NMR ([D3]acetonitrile, RT): d = 51.5 (s, N(CH3)2), 68.4 (d/m, 1J(P,C) = 158 Hz, PCH2N), 73.5 (m, NCH2CHCH2), 115.8 (s, NCH2(C6H4)CHCH2), 126.6 (s, meta-CH), 127.2 (s, para-C), 133.6 (s, ortho-CH), 135.7 (s, NCH2(C6H4)CHCH2), 139.9 ppm (s, NCH2C); 13C{19F} NMR ([D3]acetonitrile, RT): d = 120.3 (d, 2J(P,C) = 15 Hz, CF3), 120.6 ppm (d, 2J(P,C) = 24 Hz, CF3); 19F NMR ([D3]acetonitrile, RT): d = 112.2 (m, 2 F; CF2), 109.8/ 106.9 (m, 2 J(F,F) = 316 Hz, 4 F; CF2), 81.5 (m, 3 F; CF3), 80.0 (br s, 6 F; CF3), 36.6 ppm (d, 1J(P,F) = 826 Hz, 2 F; PF2); 31P NMR ([D3]acetonitrile, RT): d = 153.9 ppm (t/m, 1J(P,F) = 825 Hz, P) 31P{1H} NMR ([D3]acetonitrile, RT): d = 153.9 ppm (t/t/pseudo-quint, 1J(P,F) = 825 Hz, 2J(P,F) = 96 Hz, 2J(P,F) = 53 Hz, P); IR (solid): n˜ = 408 (w), 428 (m), 440 (m), 468 (w), 486 (m), 535 (m), 562 (s), 602 (s), 620 (s), 632 (m), 666 (s), 694 (s), 708 (s), 725 (w), 746 (m), 761 (m), 826 (s), 857 (m), 897 (w), 915 (m), 925 (m), 945 (m), 992 (m), 1019 (w), 1034 (w), 1074 (s), 1101 (s), 1111 (s), 1142 (s), 1168 (s), 1182 (s), 1208 (s), 1274 (m), 1387 (w), 1415 (w), 1445 (w), 1460 (w), 1484 (w), 1514 (w), 1612 (w), 1634 (w), 2987 (w), 3017 (w), 3040 (w), 3051 (w), 3092 cm 1 (w); MS (ESI): m/z (%): 624 (100) [M+Na] + .

P NMR (acetonitrile,

Then Me2NCH2F (0.19 g, 2.50 mmol) was added at 196 8C. The suspension was slowly warmed to room temperature. All volatile compounds were removed in vacuo. The residue was solved in acetonitrile and filtered under inert conditions. The filtrate was concentrated and diethyl ether was added. Crystallization at 30 8C yielded 7’ (1.28 g, 2.07 mmol, 83 %) as a colorless solid. 1 H NMR ([D3]acetonitrile, RT): d = 2.2 (br s, 6 H; CH3), 2.7 ppm (m, 2 H; CH2); 13C{1H} NMR ([D3]acetonitrile, RT): d = 46.8 (d/t, 3J(P,C) = 13 Hz, 4J(F,C) = 3 Hz, CH3), 65.3 ppm (d/t, 1J(P,C) = 178 Hz, 2J(F,C) = 37 Hz, CH2); 13C{19F} NMR ([D3]acetonitrile, RT): d = 120.9 (d, 2J(P,C) = 13 Hz, CF3), 121.2 ppm (d, 2J(P,C) = 25 Hz, CF3); 19F NMR ([D3]acetonitrile, RT): d = 111.7/ 109.2 (m, 2J(F,F) = 325 Hz, 4 F; CF2), 111.2 (m, 2 F; CF2), 81.1 (m, 3 F; CF3), 80.8 (s(broad), 6 F; 47.1 ppm (d/m, 1J(P,F) = 860 Hz, 2 F; PF2); 31P NMR CF3), ([D3]acetonitrile, RT): d = 149.0 ppm (t/m, 1J(P,F) = 861 Hz, P); IR (solid): n˜ = 429 (m), 476 (m), 528 (s), 548 (s), 593 (s), 613 (s), 626 (s), 643 (s), 676 (s), 710 (m), 744 (w), 844 (m), 944 (s), 992 (w), 1033 (m), 1067 (s), 1091 (m), 1103 (m), 1121 (s), 1179 (s), 1282 (m), 1426 (w), 1462 (w), 1478 (w), 1662 (w), 2795 (w), 2839 (w), 2872 (w), 2950 cm 1 (w); MS (ESI): m/z (%): 484 (100) [(C2F5)3F2PCH2NMe2] , 307 (77) [(C2F5)2F2P] , 618 (100) [M+H] + . Synthesis of [(C2F5)3F2PCH2NMe2H] (8 a): Gaseous hydrogen chloride (0.02 g, 0.68 mmol) was added to a solution of 7’ (0.34 g, 0.55 mmol) in acetonitrile (10 mL). The colorless precipitate was filtered and the filtrate was concentrated in vacuo yielding 8 a (0.24 g, 0.49 mmol, 89 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 2.9 (d, J = 5 Hz, 6 H; N(CH3)2), 3.4 (m, 2 H; CH2), 6.9 ppm (t, J = 41 Hz, 1 H; NH); 1H{31P} NMR ([D3]acetonitrile, RT): d = 2.9 (d, J = 5 Hz, 6 H; N(CH3)2), 3.4 (m, 2 H; CH2), 6.9 ppm (t, J = 41 Hz, 1 H; NH); 13C{1H} NMR ([D3]acetonitrile, RT): d = 46.4 (m, CH3), 64.5 (d/t, 1J(P,C) = 148 Hz, 2J(F,C) = 77 Hz, CH2); 13C{19F} NMR (Et2O, RT): d = 120.3 (d, 2J(P,C) = 14 Hz, CF3), 120.5 ppm (d, 2J(P,C) = 24 Hz, CF3); 19F NMR (Et2O, RT): d = 112.9/ 110.0 (m, 4 F; CF2), 112.5 (m, 2 F; CF2), 81.7 (t, J = 19 Hz, 3 F; CF3), 81.4 (m, 6 F; CF3), 44.9 ppm (d, 1J(P,F) = 806 Hz, 2 F; PF2); 31P NMR (Et2O, RT): d = 161.0 ppm (t/m, 1J(P,F) = 805 Hz, P); IR (solid): n˜ = 408 (w), 427 (m), 436 (m), 470 (w), 489 (w), 505 (w), 533 (m), 565 (s), 597 (s), 620 (s), 633 (m), 660 (s), 695 (s), 715 (m), 746 (m), 824 (m), 876 (m), 948 (s), 954 (w), 1050 (m), 1081 (s), 1121 (s), 1142 (s), 1177 (s), 1210 (s), 1281 (s), 1379 (w), 1405 (w), 1466 (w), 1483 (w), 3279 cm 1 (w); MS (ESI): m/z (%): 484 (100) [(C2F5)3F2PCH2NMe2] , 466 (100) [M F] + .

Acknowledgements Financial supported by the Deutsche Forschungsgemeinschaft (HO 2011/10-1) is gratefully acknowledged. We are grateful to Merck KGaA (Darmstadt, Germany) and Solvay (Hannover, Germany) for their support and we want to thank Dr. Julia Bader for helpful discussions.

Synthesis of [(C2F5)3F2PCH2NMe2 CH2CHCH2] (8 b): Compound 7’ (1.21 g, 1.96 mmol) was dissolved in acetonitrile (10 mL) prior to the addition of allyl bromide (0.50 g, 4.13 mmol). The reaction mixture was stirred at room temperature for 2 h until the precipitation of CsBr was completed. The suspension was filtered under inert conditions and washed with acetonitrile. Removal of the solvent yielded 8 b (1.00 g, 1.90 mmol, 97 %) as a colorless solid. 1H NMR ([D3]acetonitrile, RT): d = 3.1 ppm (s, 6 H; N(CH3)2), 3.6 (m, 2 H; PCH2N), 4.0 (d/d, 3J(H,H) = 7 Hz, 4J(P,H) = 2 Hz, 2 H; NCH2CH), 5.7 (d/ m, 3J(H,H) = 17 Hz (E), 1 H; CHCHEH), 5.7 (d/m, 3J(H,H) = 10 Hz (Z), 1 H; CHCHHZ), 6.0 ppm (d/d/t, 3J(H,H) = 17 Hz (E), 3J(H,H) = 10 Hz (Z), 3 J(H,H) = 7 Hz, 1 H; CH); 13C{1H} NMR ([D3]acetonitrile, RT): d = 52.2 (s, N(CH3)2), 63.4 (d/m, 1J(P,C) = 155 Hz, PCH2N), 71.6 (m, NCH2CHCH2), 125.5 (s, CH), 128.8 ppm (s, NCH2CHCH2); 13C{19F} NMR ([D3]acetonitrile, RT): d = 120.3 (d, 2J(P,C) = 15 Hz, CF3), 120.6 ppm (d, 2J(P,C) = 25 Hz, CF3); 19F NMR ([D3]acetonitrile, RT): d = 112.1 (m, 2 F; CF2), 109.9/ 106.9 (m, 2J(F,F) = 316 Hz, 4 F; CF2), 81.5 (m, 3 F; CF3), 80.0 (br s, 6 F; CF3), 37.0 ppm (d, 1J(P,F) = 823 Hz, 2 F; PF2); 31P NMR ([D3]acetonitrile, RT): d = 154.0 ppm (t/m, 1J(P,F) = 824 Hz, P) 31P{1H} NMR ([D3]acetonitrile, RT): d = 154.0 ppm (t/t/ Chem. Eur. J. 2014, 20, 1 – 11

www.chemeurj.org


Keywords: fluorine · iminium phosphate · phosphorus

·

oxidative

addition

·

[1] D. Guyomard, J. M. Tarascon, (Bell Communications Research, Inc., USA), US 5192629A. [2] a) R. P. Swatloski, J. D. Holbrey, R. D. Rogers, Green Chem. 2003, 5, 361 – 363; b) A. V. Plakhotnyk, L. Ernst, R. Schmutzler, J. Fluorine Chem. 2005, 126, 27 – 31; c) M. Ponikvar, B. Zˇemva, J. F. Liebman, J. Fluorine Chem. 2003, 123, 217 – 220. [3] a) M. Schmidt, U. Heider, A. Kuehner, R. Oesten, M. Jungnitz, N. Ignat’ev, P. Sartori, J. Power Sources 2001, 97 – 98, 557 – 560; b) N. Ignatiev, P. Sartori, DE 19641138A1. [4] V. Aravindan, J. Gnanaraj, S. Madhavi, H.-K. Liu, Chem. Eur. J. 2011, 17, 14326 – 14346.

9


&

&

Full Paper [5] W. Xie, C. D. Frisbie, J. Phys. Chem. C 2011, 115, 14360 – 14368. [6] R. Gonzlez, A. Hernndez Battez, D. Blanco, J. L. Viesca, A. FernndezGonzlez, Tribol. Lett. 2010, 40, 269 – 277. [7] N. Ignatyev, M. Schulte, J. Bader, B. Hoge, WO 2011/072810A1, Merck Patent GmbH, Darmstadt. [8] N. Ignatyev, G. Bissky, H. Willner, (Merck Patent GmbH, Darmstadt), WO 2008/092489A1. [9] B. Hoge, J. Bader, N. Ignatyev, M. Schulte, (Merck Patent GmbH, Darmstadt), WO 2012/041431A1; B. Hoge, J. Bader, N. Ignatyev, M. Schulte, W. Hierse, W. Wiebe, H. Willner, (Merck Patent GmbH, Darmstadt), WO 2012/048772A1. [10] a) N. Ignat’ev, P. Sartori, J. Fluorine Chem. 2000, 103, 57 – 61; b) U. Heider, V. Hilarius, P. Sartori, N. Ignat’ev, (Merck Patent GmbH, Darmstadt), WO 00/21969. [11] a) I. P. Komkov, S. Z. Ivin, K. V. Karavanov, L. Ye Smirnov, Z. Obshchei Khim. 1962, 32, 301; b) R. Schmutzler, Chem. Ind. 1962, 1868 – 1869; c) R. Schmutzler, Inorg. Chem. 1964, 3, 410. [12] a) J. F. Nixon, J. Inorg. Nucl. Chem. 1969, 31, 1615 – 1619; b) A. A. Kolomeitsev, F. U. Seifert, G.-V. Rçschenthaler, J. Fluorine Chem. 1995, 71, 47 – 49; c) M. Gçrg, G.-V. Rçschenthaler, A. A. Kolomeitsev, J. Fluorine Chem. 1996, 79, 103 – 104. [13] T. Bçttcher, O. Shyshkov, M. Bremer, B. S. Bassil, G.-V. Rçschenthaler, Organometallics 2012, 31, 1278 – 1280. [14] H. Bçhme, M. Hilp, Chem. Ber. 1970, 103, 104 – 111. [15] S. M. Igumnov, N. I. Delyagina, Y. V. Zeifman, I. L. Knunyants, Russ. Chem. Bull. 1981, 30, 637 – 639.

&

&

Chem. Eur. J. 2014, 20, 1 – 11

www.chemeurj.org

[16] K. O. Christe, D. A. Dixon, H. P. A. Mercier, J. C. P. Sanders, G. J. Schrobilgen, W. W. Wilson, J. Am. Chem. Soc. 1994, 116, 2850 – 2858. [17] H. Bçhme, M. Haake, Justus Liebigs Ann. Chem. 1967, 705, 147 – 153. [18] N. V. Ignat’ev, U. Welz-Biermann, A. Kucheryna, G. Bissky, H. Willner, J. Fluorine Chem. 2005, 126, 1150 – 1159. [19] K. L. Lundberg, R. J. Rowatt, N. E. Miller, Inorg. Chem. 1969, 8, 1336 – 1340. [20] G. R. Clark, G. L. Shaw, P. W. J. Surman, M. J. Taylor, D. Steele, J. Chem. Soc. Faraday Trans. 1994, 90, 3139 – 3144. [21] A. R. Mahjoub, D. Leopold, K. Seppelt, Z. Anorg. Allg. Chem. 1992, 618, 83 – 88. [22] O. A. Shyshkov, Ph.D. thesis, Universitt Bremen, Bremen, 2006. [23] N. Allefeld, B. Neumann, H.-G. Stammler, B. Hoge, unpublished results. [24] A. V. Zakharov, Y. V. Vishnevskiy, N. Allefeld, J. Bader, B. Kurscheid, S. Steinhauer, B. Hoge, B. Neumann, H.-G. Stammler, R. J. F. Berger, N. W. Mitzel, Eur. J. Inorg. Chem. 2013, 3392 – 3404. [25] U. Welz-Biermann, (Merck Patent GmbH, Darmstadt), WO 03/087113A1. [26] O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann, J. Appl. Crystallogr. 2009, 42, 339 – 341. [27] G. M. Sheldrick, Acta Crystallogr. Sect. A 2008, 64, 112 – 122.

Received: February 28, 2014 Published online on && &&, 0000

10



Full Paper

FULL PAPER & Fluorine Chemistry N. Allefeld, B. Neumann, H.-G. Stammler, G.-V. Rçschenthaler, N. Ignat’ev, B. Hoge* && – && It’s down to the fluorine: Several novel functionalized perfluoroalkylfluorophosphates were synthesized via an efficient one-pot synthesis, employing Me2NCH2F as an oxidizer. Following treatment with

electrophiles (R X), such as HCl or allyl bromides, leads to the formation of zwitterionic ammonium phosphates (see scheme).

Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates

In this chemical puzzle……fluoromethyldimethylamine represents a versatile reactant for the synthesis of electron-deficient, functionalized phosphates. Thus, the oxidative addition of the reagent to (C2F5)nPF3 n (n = 1– 3) selectively affords zwitterionic [(C2F5)nF5 nP(CH2NMe2 CH2NMe2)] (n = 1–3) in good yields. The course of the reaction involved the phosphoranide [P(C2F5)3F] , which was evidenced independently. Treatment of [(C2F5)3F2P(CH2NMe2 CH2NMe2)] with aqueous sodium hydroxide gave rise to the formation of the phosphate Na + [(C2F5)3F2P(CH2NMe2)] . The nucleophilic nitrogen atom in the phosphates [(C2F5)nF5 nP(CH2NMe2)] allows the synthesis of several novel functionalized perfluoroalkylfluorophosphates. See the Full Paper by B. Hoge et al. for more details.

Chem. Eur. J. 2014, 20, 1 – 11

www.chemeurj.org


11


&

&

Synthesis, Characterization, and Reactivity of Functionalized Trinuclear Iron-Sulfur Clusters - A New Class of Bioinspired Hydrogenase Models.

Synthesis, reactivity, and biological activity of gold(I) complexes modified with thiourea-functionalized tyrosine kinase inhibitors.

Synthesis and Reactivity of Triazaphenanthrenes.

Synthesis and characterization of naphthalimide-functionalized polynorbornenes.

Ynol Ethers: Synthesis and Reactivity.

Efficient and modular synthesis of new structurally diverse functionalized [n]paracyclophanes by a ring-distortion strategy.

Synthesis and reactivity of carbachlorins and carbaporphyrins.

Synthesis and Antimycobacterial Activity of some Triazole Derivatives-New Route to Functionalized Triazolopyridazines.

Synthesis, characterization, and biological evaluation of some new functionalized terphenyl derivatives.

Dichlorocarbene-Functionalized Fluorographene: Synthesis and Reaction Mechanism.

Synthesis, structural characterization and reactivity of heteroazuliporphyrins.

Synthesis and Reactivity of Discrete Calcium Imides.

Synthesis of neoglycosphingolipid from methoxyamino-functionalized ceramide.

A new synthesis of brassinosteroids with a cholestane framework based on a highly functionalized starting material.

Synthesis of functionalized cyanopyrazoles via magnesium bases.

Efficient synthesis of ABAB functionalized phthalocyanines.

Towards potential nanoparticle contrast agents: Synthesis of new functionalized PEG bisphosphonates.

m-Metallaphenol: synthesis and reactivity studies.

Digermylene oxide complexes: facile synthesis and reactivity.

Chiral hypervalent iodine reagents: synthesis and reactivity.

New aryloxybenzylidene ruthenium chelates - synthesis, reactivity and catalytic performance in ROMP.

Zinc(II)-methimazole complexes: synthesis and reactivity.

Synthesis and optical properties of dioxolane-functionalized hexacenes and heptacenes.

Synthesis and derivatization of highly-functionalized λ⁵-phospholes.