Synthesis and the structure of 8-tetrahydrofuronium and 8-tetrahydropyronium derivatives of iron bis(dicarbollide)(-I) and their cleavage reactions.

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Page 1 of 72

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DOI: 10.1039/C4DT03015J

Synthesis and structure of 8-tetrahydrofuronium and 8-tetrahydropyronium derivatives of iron bis(dicarbollide)(-I) and their cleavage reactions. Design of

Irina Lobanovaa, Irina Kosenkoa, Julia Laskovaa, Ivan Ananyeva, Anna Druzinaa, Ivan Godovikova, Vladimir I. Bregadzea, Shicheng Qib, Zbigniew J. Leśnikowskic and Andrey Semioshkina*

Abstract.

8-Tetrahydrofuronium

and

8-tetrahydropyronium

derivatives

of

iron

bis(dicarbollide)(-I) were synthesized. Their reactions of ring cleavage by MeOH, N3-, amines and 1,2-bis(diphenylphosphino)ethane were investigated. 8-Tetrahydrofuronium iron bis(dicarbollide)(-I) was found to be more active in these reactions in comparison to 8-tetrahydropyronium and 8-dioxonium species, respectively. First conjugates of iron bis(1,2-dicarbollide)(-I) with 2’-deoxyadenosine modified via C-8 position of the purine base were synthesized. Reactions of

these oxonium compounds

with 1,2-

bis(diphenylphosphino)ethane (dppe) led to zwitter-ionic monophosphonium salts. One of these compounds has given rise to novel ferracarborane/cobaltacarborane hybride complex.

1

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Published on 19 November 2014. Downloaded by Simon Fraser University on 21/11/2014 07:43:49.

novel ferracarborane ligands and nucleoside conjugates .†‡

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Page 2 of 72 View Article Online

DOI: 10.1039/C4DT03015J

Introduction Following the discoveries of Hawthorne,1,2 metallacarboranes like cobalt bis(1,2dicarbollide)(-I) and iron-bis(1,2-dicarbollide)(-I) (1) are of increased interest for many

extraction agents,5 semiconductor materials,6 HIV protease inhibitors,7 boron labels of DNA fragments8 and new conducting organic polymers.9 Cyclic oxonium derivatives of cobalt bis(1,2-dicarbollide)(-I) became versatile building blocks for the preparation of many organic and bioorganic conjugates via oxonium ring cleavage reactions.10 Contrary to cobalt bis(1,2-dicarbollide)(-I), investigation of cyclic oxonium derivatives of the iron-bis(1,2-dicarbollide)(-I) (1) was significantly limited. Synthesis and structure of 8-dioxonium iron bis(1,2-dicarbollide)(-I) (2) (Fig. 1) was first reported by Plešek et al.11

Fig. 1. Compound 2 was prepared by the action of dimethylsulfate in 1,4-dioxane on iron bis(dicarbollide)(-I) with a good yield (Fig. 1).11 Its ring cleavage reactions with OH-, ammonia, pyridine, 4-formylpyridine, 2-methoxyphenole, 1-naphthamide and Ph3P were reported.11,12 Reaction of 2 at 6-N of the exo-amino group of protected deoxyadenosine has afforded the first conjugate of iron bis(1,2-dicarbollide)(-I) with nucleosides.13 Two other nucleoside conjugates of iron bis(1,2-dicarbollide)(-I) were designed by cleavage of 2 with NaN3

followed by “click” reaction of the resultant azide with nucleosides 2



aspects of fundamental and applied chemistry.3,4 Representative applications include

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bearing terminal alkyne group.14 Recently the same approach was used to prepare the DNA probe modified with iron-bis(1,2-dicarbollide)(-I) for electrochemical determination of DNA sequence of UL55 gene of human cytomegalovirus (HCMV)15 and Avian

Herein

we

report

synthesis

and

reactivity

investigations

of

the

8-

tetrahydrofuronium and 8-tetrahydropyronium derivatives of iron bis(dicarbollide)(-I) and synthesis of its novel ligands and nucleoside conjugates.

3



Influenza Virus H5N1.16

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Results and discussion Inspired by the report of Plešek about synthesis and some cleavage reactions of 8-dioxonium iron bis(1,2-dicarbollide)(-I) (2),11 we have focused first on the synthesis of

successfully reproduced the described protocol for the preparation of the complex 2 by heating of [1]Cs in dioxane with double molar excess of (MeO)2SO2 for three hours.11 However reactions of [1]Cs with tetrahydrofurane and tetrahydropyrane under the same conditions proceeded much slower, starting material ([1]Cs) was still remaining after 10 hours of heating according to a TLC analysis of the reaction mixture. Thus, we have modified the above protocol. We have found that heating of [1]Cs in tetrahydrofurane or tetrahydropyrane with a twentyfold molar excess of dimethylsulfate led efficiently to desired oxonium derivatives of iron bis(1,2-dicarbollide)(-I) 3, and 4 respectively (Scheme 1).

Scheme 1. However, it was found that the adduct with tetrahydrofurane (3) was unstable in the solutions, therefore the isolated yield of it was only 47%, yet the yield of the tetrahydropironium derivative was almost quantitative. The structures of 3-4 was proved by NMR spectroscopy. In the

11

B NMR the observed patterns were practically the same

as described for the compound 211 (see experimental). In the 1H NMR of 3, 4 the signals of B(8)-O+(CH2)2 protons were detected in the high field as broad singlets at δ = -10.80 4



the analogous complexes with another cyclic ethers. It is to be noted that we have

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and -13.77 ppm, respectively, due to the paramagnetism of FeIII in these complexes. The signals for CH-groups of the boron cages were observed in 1H NMR as broad singlet at δ = 29.57 ppm in the case of 3. In the complex 4 these groups appeared as

reported ones for the compound 2.11 The signals of CH-groups in

13

C NMR of 3 and 4

were observed at the low filed at ca. -330 and -400 ppm due to the paramagnetism of FeIII as well. Finally, the molecular structure of tetrahydrofuronium derivative 3 was determined by single-crystal X-ray diffraction (Fig. 2).

Fig. 2. ORTEP representation of the molecular structure of 3; thermal ellipsoids are drawn with 50% probability level. Selected bond lengths and torsion angles in two independent molecules of 3: Ccarb-Ccarb 1.598(7) - 1.614(6) Å, B-O 1.493(6) and 1.502(7) Å, C-O 1.483(6) - 1.497(6) Å, C(3)-C(4)-C(5)-C(6) 42.0(5)° and 37.1(6)°, HC(1)…C(1A)H 48.1(5)° and 61.2(5)°, skew angles are less than 2°.

The subsequent studies of the reactivity of 2-4 towards various nucleophiles have shown that tetrahydrofuronium derivative (3) is much more active than compounds 2 and 4. Thus, stirring of 3 in methanol for one hour led to CH3O- cleavage product. It was 5



two broad singlets (δ = 26.14 and 18.51 ppm) and these values perfectly match to the

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isolated as Cs-salt ([5]Cs) with a good yield (Scheme 2). Contrary to 3, complexes 2 and 4 were found to be inert towards methanol under the same conditions. Previously Lesnikowski et. al. has reported the reaction of 2 with sodium azide in

have found that complexes 3 and 4 react with NaN3 in boiling ethanol to give corresponding azides as well. Reaction of the complex 3 has proceeded just within five minutes only, however in the case of 4 one hour heating was required to complete the conversion. These azides were also obtained as Cs-salts ([6, 7]Cs) with good yields.

Scheme 2: i: MeOH, 1 h, RT, then CsCl/H2O; ii: NaN3, EtOH, 5 min reflux; iii: NaN3, EtOH, 60 min reflux, then CsCl/H2O. Reactions of 2-4 with morpholine led to corresponding ammonium salts 8-10 (Scheme 3). These reactions were carried out in mesitylene at 80°C. Reaction of 3 has taken just 5 minutes and reactions of 4 and 2 have taken 30 and 40 min, respectively.

6



DMFA to give [(1,2-C2B9H11)-3,3’-Fe-(1’,2’-C2B9H10)-8-O(CH2)2O(CH2)2N3]Na.14 We

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Scheme 3. i: morpholine, mesitylene, 80°C. An interesting observation was made analyzing the

13

C-NMR spectra of 8-10. In

the case of compound 9 the signal of B(8)-OCH2 group was observed at δ=11.3 ppm. The similar δ-values of these groups were found for the compounds 5-7 as well as for the previously described ring-cleavage products of 2.11 Characteristic high field high field shifting of B(8)-OCH2 group caused by the paramagnetism of FeIII was observed for all of these compounds. However, the signals of B(8)-OCH2 groups in the

13

C-NMR

spectra of the adducts 8 and 10 were detected at δ = 72.9 and 39.2 ppm respectively in acetone-d6 (Fig. 3).

7



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Fig. 3. Fragments of

13

C NMR spectra of 8 in acetone-d6 (a), 8 in DMSO-d6 (b), 9 in

acetone-d6 (c) and 10 in acetone-d6 (d).

We hypothesize that the observed low field shifting can be ascribed to the intramolecular interaction or H-bonding between B(8)-O and N-H+ in these compounds (Fig. 4) in acetone-d6 solution. -1

-1

O Fe

Fe O H

O

+

N

H

O

8

N+ O

10

Fig. 4. 8



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Previously we have observed and proved that such H-bonding takes place in the similar compounds, but bearing closo-dodecaborate(-II) boron cluster.17 We have also recorded

13

C-NMR spectra of 8 and 10 in DMSO-d6. In this solvent the signals of B(8)-

shifts were 31.4 and 29.9 ppm respectively indicating indirectly decrease of such intramolecular interaction in the more polar solvent. Molecular structures of the compounds 8 and 9, determined by single-crystal Xray diffraction (Fig. 5), also presented an unambiguous evidence of H-bonding effects. Thus, hydrogen bonds were observed in crystals of both compounds, although these interactions are of different character. In 8 the rather strong intramolecular interaction between NH fragment and the O(1) oxygen atom (O(1)…N(1) 2.646(2) - 2.728(3) Å, O(1)…H(1N)-N(1) 143 - 168° in three independent molecules) leads to the formation of the seven-membered H-bonded cycle with a chair conformation. Corresponding proximity of the morpholine and dicarbollide fragments in 8 agrees well with chemical shifts observed in solution by NMR spectroscopy. In turn, there are only two intermolecular H-bonds between the substituted metallacarborane moiety and a solvate water molecule in the crystal of 9 (N(1)…O(1W) 2.7421(17) Å, N(1)-H(1)…O(1W) 159°, O(1W)…O(1) 2.7483(16) Å, O(1W)-H(1WB)…O(1) 166°). One can suppose that the increased length of the hydrocarbon spacer in 9 makes a structure with direct intramolecular H-bond less favorable. Furthermore, the less hindered conformation of the substituent can be additionally stabilized by interactions between hydrogen donor/acceptor fragments and a water molecule, that makes negligible the influence of morpholine moiety on the B(8)-OCH2 group. The presence of a H2O molecule acting as a bridge match with a reported postulate18 that oxygen atom in the B(8)–O fragment can dissipate the negative charge of the metallacarborane anion and becomes a strong Lewis base. 9



OCH2 groups of 8 and 10 were found in the higher field than in acetone-d6. Chemical

Dalton Transactions


a

b

Fig 5. ORTEP representation of the molecular structures of 8 (a) and 9 (b); thermal ellipsoids are drawn with 30% probability level for 8 and with 50% level for 9; dashed lines correspond to H-bonds. Selected bond lengths and angles in three independent molecules

of

8:

Ccarb-Ccarb

1.595(3)-1.615(3)

Å,

B-O

1.437(3)-1.443(3)

Å,

HC(1)…C(2A)H 51.9(5)°, 55.8(5)° and 104.1(6)°, skew angles are not more than 3°. Selected bond lengths and angles in 9: Ccarb-Ccarb 1.622(2) and 1.638(2) Å, B(9)-O(1) 1.4274(18) Å, O(1)-C(3) 1.4328(17) Å, H-C(1)…C(1A)-H 118.8(4)°, skew angle is 2.0(4)°

Compounds 2-4 were also found to react with tertiary alkylamines (2(dimethylamino)ethanol and N,N-dimethylprop-2-yn-1-amine) to afford corresponding zwitter-ionic quaternary ammonium salts 11-16 (Scheme 4).

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Scheme 4. i: Me2NCH2CH2OH/CH3CN; ii: Me2NCH2C≡CH/CH3CN. These reactions proceeded rapidly in CH3CN solution with excellent yields. Compound 3 has reacted with these species instantly and in the case of 4 and 2 only 10 min heating has been required to complete conversion. Thus, we have used this methodology for the preparation of the novel iron bis(1,2-dicarbollide)(-I) nucleoside conjugates. Design of such compounds is important because boronated nucleosides are considered to be potential boron carriers for the boron neutron capture therapy (BNCT) of tumors19,20 and offer many other possible applications.21 Reactions of cyclic oxonium derivatives of closo-dodecaborate(-II)17 and cobalt bis(1,2-dicarbollide)(-I)22 with alkylamines have given us recently a straightforward access to a series of novel nucleoside conjugates of these boron clusters.23,24 Expanding this approach we have found that complexes 2-4 react with 8-(2-dimethylaminoethyl)-amino-2’-deoxyadenosine (17) leading to the new conjugates of iron bis(1,2-dicarbollide)(-I) with 2’deoxyadenosine 18-20 (Scheme 5).

11



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-1

-1

NH2

Fe

Fe


O+

O

N+

18

N

O OH

-1

-1

Y

Fe

N

N

HO

3

N

H N

i

NH2

Fe O

O+

Y

N+

HO 19, Y=CH2 20, Y=O

4, Y=CH2 2, Y=O

N N H

N

N N

O OH

NH2 N

N

N H

HO

N

N N

O OH

17

Scheme 5. i: 17, CH3CN, reflux Compounds 18-20 are first conjugates of iron bis(1,2-dicarbollide)(-I) with 2’deoxyadenosine modified at C-8 position of the purine base. In the case of compounds reported previously the linkage was achieved either at 6-N of the exo-amine group of the nucleobase13 or at 2’-position of the ribose.14 The other interesting aspect of metallacarborane chemistry is a ligand design for homogeneous C-C coupling reactions and for the synthesis of new metal complexes.25 We have found that compounds 3, 4 and 2 react with bis(diphenylphosphino)ethane (dppe) to give corresponding zwitter-ionic monophosphonium salts 21-23 (Scheme 6).

12


i

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Scheme 6, i: dppe, mesitylene, 80°C. The structure of the compound 21 was determined by single-crystal X-ray diffraction (Fig. 6).

13



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Fig 6. ORTEP representation of the molecular structure of 21; thermal ellipsoids are drawn with 30% probability level. Selected bond lengths and angles in 21: Ccarb-Ccarb 1.590(4) and 1.629(5), B(9)-O(1) 1.413(4), H-C(1)…C(1A)-H 161.0(5), skew angle is 1.4(4).

Compounds 21-23 were applied then for the preparation of the novel heterometal complexes. Thus, 22 was found to react with iodonium-bridged derivative of cobalt bis(1,2-dicarbollide)(-I) (8,8’-µ-I-3,3’-Co(1,2-C2B9H10)2 (24) to give highly boron-rich compound 25 (Scheme 6).

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-1

-1


O

Ph

P+

Ph

+

Co

I+

Ph

P Ph

22

24 -1 -1

Fe

Ph O

Ph P+ P+ Ph Ph

Co I

25

Scheme 6 This compound is the first example of the species containing cobalt bis(1,2dicarbollide)(-I) and iron-bis(1,2-dicarbollide)(-I) in one molecule. Design of this new type of molecules containing various metals is ongoing in our laboratories for different prospective applications.

Conclusion Synthesis and ring-cleavage reactions of oxonium derivatives of iron bis(dicarbollide)(-I) pens prospectives for the design of biogconjugates and new materials bearing this maetallacarborane. Clear relationship between the susceptibility of the oxonium derivatives of iron bis(dicarbollide)(-I) to the nucleophilic ring cleavage and the structure of the cyclic ether was observed. The reactivity of the adducts 2-4 changes in the order: 3 (tetrahydrofuronium) > 4 (tetrahydropironium) ≈ 2 (dioxonium) and this is in agreement with cyclic ethers reactivity. 15


Fe

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Acknowledgements Authors are grateful to Russian Science Foundation for Basic Research (Grants 14-03-

Russian Academy of Sciences "Development of Methods for the Synthesis of Chemical Substances and Design of New Materials" (Program P-8), Foundation for the Development of Small Business in Science (Grant SMARTY 0002237) for financial support (AD). Partial contribution of the Statutory Fund of IMB PAS (ZJL) is gratefully acknowledged.

16



31029 (IK), 14-03-31382 (JL), 14-03-00042 (IL, AS)), program of the Presidium of the

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Experimental Materials and methods. Chemicals were reagent grade and received from standard commercial vendors. Cs[3,3’-Fe(1,2-C2B9H10)2]

(Cs[1]),2

8-O(C2H4)2O-3,3’-Fe(1,2-C2B9H10)2

(2),11 dimethylaminoethyl)-amino-2’-deoxyadenosine (11)23 and (8,8’-µ-I-3,3’-Co(1,2C2B9H10)2 (24)26 were prepared as described. Acetonitrile was distilled from P2O5 and then from CaH2. THF, tetrahydropyrane and 1,4-dioxane were distilled from Na/benzophenone prior before use. TLC was performed on Kieselgel 60 F245 (Merck) plates. Column chromatography was made on Silica gel 60 0.060-0.200 (Acros Organics). The 1H,

13

C and

11

B NMR spectra were recorded at 400.13, 100.61 and

128.38 MHz, respectively, on a BRUKER-Avance-400 spectrometer. Tetramethylsilane and BF3/Et2O were used as standards for 1H and

13

C NMR, and

11

B NMR, respectively.

All chemical shifts are reported in ppm (δ) relative to external standards. High resolution mass spectra (HR MS) were measured on a Bruker micrOTOF II instrument using electrospray ionization (ESI). The measurements were done in a positive ion mode (interface capillary voltage – 4500 V) or in a negative ion mode (3200 V); mass range from m/z 50 to m/z 3000 Da; external or internal calibration was done with Electrospray Calibrant Solution (Fluka). A syringe injection was used for solutions in acetonitrile, methanol, or water (flow rate 3 µL/min). Nitrogen was applied as a dry gas; interface temperature was set at 180°C. The theoretical MS values were calculated using Compass Analysis (v. 4.0) software (Bruker Daltonics). IR-FT spectra were recorded on Infralum FT-801 FT-IR spectrometer in Nujol. Elemental analysis was performed in Microanalytical laboratory of A.N. Nesmeyanov Institute of Organoelement Compounds. Crystals of the compounds 3, 8, 9 and 21 were grown from the CH2Cl2-hexane mixture.

17



Compounds

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Synthetic procedures Oxonium derivatives of iron-bis(dicarbollide) (-I) (3-4), general procedure. To a solution of 300 mg (0.66 mmol) of [1]Cs in 15 mL of abs. THF, tetrahydropyrane or

refluxed for 3 h. Then the volatiles were removed in vacuum and products 2-3 were purified by silica gel column chromatography eluting with CH2Cl2. 8-(Terahyrofuronium-1-yl)-(H)-1,1’,2,2’-tetracarba-3-commo-ferra-closotricosaborate (3). Yield 120 mg (46%) as carmine crystals. Found (%): C, 24.29; H, 7.41. C8H29B18FeO requires (%): C, 24.53; H, 7.46. 1H NMR (acetone-d6, δ, ppm): 29.57 (br. s, 4H, CH-carborane), 2.41 (br. s, 4H, CH2), -10.80 (br. s, 4H, CH2O).

13

C NMR

(CD2Cl2, δ, ppm): 80.5 (B-OCH2), 14.7 (CH2), -373.1 (C-carborane), -431.2 (Ccarborane).

11

B NMR (acetone-d6, δ, ppm): 110.9 105.2, 7.2, 5.5, 3.9, -5.7, -14.9, -26.7,

-38.4, -339.6, -418.6, -487.8, -625.8. IR-FT (nujol, ν, cm-1): 2554 (BH). . HRESIMS: found 415.3177. C8H29B18FeO+Na requires: 415.3250. 8-(Terahyropyronium-1-yl)-(H)-1,1’,2,2’-tetracarba-3-commo-ferra-closotricosaborate (4). Yield 260 mg (96%) as claret crystals. Found (%): C, 26.37; H, 7.65. C9H31B18FeO: requires (%): C, 26.64; H, 7.70. 1H NMR (acetone-d6, δ, ppm): 26.14 (br. s, 2H, CH-carborane), 18.51 (br. s, 2H, CH-carborane), 2.06 (br. s, 4H, CH2), 1.92 (br. s, 2H, CH2), -13.85 (br. s, 4H, CH2O). 13C NMR (acetone-d6, δ, ppm): 86.5 (CH2O), 11.8 (CH2), 6.7 (CH2), -329.6 (C-carborane), -399.2 (C-carborane).

11

B NMR (acetone-d6, δ,

ppm): 110.9, 105.2, 7.2, 5.5, 3.9, -5.8, -26.7, -38.4, -339.6, -418.6, -487.8, -625.8. IR-FT (nujol, ν, cm-1): 2549 (BH). HRESIMS: found: 429.3411. C9H31B18FeO+Na requires 429.3407. 8-(4-(Methoxybutoxy)-1,1’,2,2’-tetracarba-3-commo-ferra-closo-tricosaborate ([5]Cs). A solution of 80 mg (0.20 mmol) of 3 was stirred at the RT for 1 h. Then the volatiles were removed in vacuum, the rest was dissolved in 3 mL of acetone To the 18



1,4-dioxane 1.2 mL (12.68 mmol) of dimethylsulfate was added and the mixture was

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resulting solution 1 g of CsCl in 100 mL of water was quenched. Crude product was filtered, air dried and purified by silica gel column chromatography eluting with CH2Cl2/CH3CN 5/1 v/v. Yield 80 mg (93%) as a brown foam. Found (%): C, 19.38; H,

61.02 (br. s, 2H, CH-carborane), 27.54 (br. s, 2H, CH-carborane). 13C NMR (acetone-d6, δ, ppm): 65.4 (CH2O), 54.3 (CH3O), 13.9 (CH2), 11.3 (CH2), 5.9 (CH2OB), -509.7 (Ccarborane), -554.6 (C-carborane).

11

B NMR (acetone-d6, δ, ppm): 118.4, 101.0, 43.5,

30.4, -1.8, -6.7, -40.8, -362.2, -365.5, -441.6, -475.2. HRESIMS: found: 423.3541. C9H32B18FeO2 requires 423.3548. Reactions of 3-4 with NaN3, general procedure. Synthesis of 6-7. A solution of 1 mmol of 3-4 and 2.5 mmol NaN3 in 10 mL of 96% ethanol was refluxed for 5 min (3) or 1 hour (4). Then the volatiles were removed in vacuum, the rest was dissolved in 3 mL of acetone To the resulting solution 1 g of CsCl in 100 mL of water was quenched. Crude products were filtered and purified by silica gel column chromatography eluting with CH2Cl2/CH3CN 5/1 v/v. 8-(4-Azidobutoxy)-1,1’,2,2’-tetracarba-3-commo-ferra-closo-tricosaborate

(6).

Prepared from 80 mg (0.20 mmol) of 3 and 33 mg (0.51 mmol) of NaN3. Yield 100 mg (86%) as a brown foam. Found (%): C, 16.72; H, 5.14; N, 7.36. C8H29N3B18CsFeO requires (%): C, 16.96; H, 5.16; N, 7.42. 1H NMR (acetone-d6, δ, ppm): 62.41 (br. s, 2H, CH-carborane), 28.60 (br. s, 2H, CH-carborane).

13

C NMR (acetone-d6, δ, ppm): 44.0

(CH2N3), 13.2 (CH2), 11.9 (CH2), 5.4 (CH2OB), -505.9 (C-carborane), -549.2 (Ccarborane).

11

B NMR (acetone-d6, δ, ppm): 117.9, 100.7, 42.9, 29.8, -1.7, -14.1, -6.9, -

40.5, -53.0, -362.7, -366.7, -424.0, -439.5, -476.5. IR-FT (nujol, ν, cm-1): 2564 (BH), 2103 (N3). HRESIMS: found 434.3460; C8H29N3B18FeO requires 434.3456.

19



5.77. C9H32B18CsFeO2 requires (%): C, 19.45; H, 5.80. 1H NMR (acetone-d6, δ, ppm):

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8-(5-Azidopentoxy)-1,1’,2,2’-tetracarba-3-commo-ferra-closo-tricosaborate ([7]Cs). Prepared from 110 mg (0.27 mmol) of 4 and 45 mg (0.69 mmol) of NaN3. Yield 100 mg (64%) as a brown foam. Found (%): C, 18.37; H, 5.41; N, 7.19. C9H31N3B18CsFeO

CH-carborane), 27.90 (br. s, 2H, CH-carborane).

13

C NMR (acetone-d6, δ, ppm): 46.8

(CH2N3), 21.6 (CH2), 14.1 (CH2), 10.6 (CH2), 5.8 (CH2OB), -509.7 (C-carborane), -555.5 (C-carborane). 11B NMR (acetone-d6, δ, ppm): 119.0, 101.6, 43.3, 30.3, -1.7, -6.6, -40.8, -367.5, -379.0, -448.3, -479.8. IR-FT (nujol, ν, cm-1): 2567 (BH), 2100 (N3). HRESIMS: found 448.3600; C9H31N3B18FeO requires 448.3613. Reactions of 2-4 with morpholine, general procedure. Synthesis of 8-10. To a solution of 1 mmol of 2-4 in 10 mL of abs. mesitylene 1.1 mmol of morpholine was added and the mixture was heated at 80°C for 5 (3), 30 (4) or 40 min (2). Then the solution was cooled and then 100 mL of hexane was added and the mixture was stored at -20°C overnight. The precipitates were filtered and then purified by silica gel column chromatography eluting with CH2Cl2/CH3CN 1/1 v/v. 8-(4-(Morpholinium)butoxy)-1,1’,2,2’-tetracarba-3-commo-ferra-closotricosaborate (8). Prepared from 120 mg (0.30 mmol) of 3 and 0.03 mL (0.34 mmol) of morpholine. Yield 80 mg (55%) as a red-brown foam. Found (%): C, 29.84; H, 8.03; N, 2.89. C12H38NB18FeO2 requires (%): C, 30.10; H, 8.00; N, 2.92. 1H NMR (acetone-d6, δ, ppm): 35.44 (br. s, 2H, CH-carborane), 32.73 (br. s, 2H, CH-carborane).

13

C NMR

(acetone-d6, δ, ppm): 72.9 (B-OCH2), 58.2 (CH2O), 49.0 (CH2N), 43.5 (CH2N), 16.2 (CH2), 10.9 (CH2), -409.1 (C-carborane), -420.0 (C-carborane). 11B NMR (acetone-d6, δ, ppm):112.8, 104.6, 14.5, 0.2, -1.1, -2.8, -3.9, -29.4, -39.9, -400.5, -440.9, -452.3, -525.8. IR-FT (nujol, ν, cm-1): 2535 (BH). HRESIMS: found 478.3968; C12H36NB18FeO2 (M-2H) requires 478.3961.

20



requires (%): C, 18.62; H, 5.38; N, 7.24. 1H NMR (acetone-d6, δ, ppm): 61.33 (br. s, 2H,

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DOI: 10.1039/C4DT03015J

8-(5-(Morpholinium)pentoxy)-1,1’,2,2’-tetracarba-3-commo-ferra-closotricosaborate (9). Prepared from 120 mg (0.25 mmol) of 4 and 0.03 mL (0.34 mmol) of morpholine. Yield 120 mg (82%) as a red-brown foam. Found (%): C, 31.42; H, 8.15; N,

ppm): 65.96 (br. s, 2H, CH-carborane), 31.65 (br. s, 2H, CH-carborane).

13

C NMR

(acetone-d6, δ, ppm): 62.3 (CH2O), 53.0 (CH2N), 50.2 (CH2N), 16.2 (CH2), 14.2 (CH2), 11.3 (B-OCH2), 10.2 (CH2), -493.5 (C-carborane), -534.8 (C-carborane).

11

B NMR

(acetone-d6, δ, ppm): 118.4, 100.9, 38.0, 27.8, -1.8, -6.4, -39.2, -369.7, -380.0, -446.3, 484.6. IR-FT (nujol, ν, cm-1): 3605 (H2O), 2534 (BH). HRESIMS: found 494.4264; C13H40NB18FeO2+H requires 494.4275. 8-(2-(2-(2-Morpholinium)ethoxy)ethoxy)-1,1’,2,2’-tetracarba-3-commo-ferra-closotricosaborate (10). Prepared from 150 mg (0.37 mmol) of 2 and 0.035 mL (0.40 mmol) of morpholine. Yield 150 mg (83%) as a red-brown foam. Found (%): C, 28.96; H, 7.71; N, 2.80. C12H38NB18FeO3 requires (%): C, 29.13; H, 7.74; N, 2.83. 1H NMR (acetone-d6, δ, ppm): 41.88 (br. s, 2H, CH-carborane), 28.00 (br. s, 2H, CH-carborane).

13

C NMR

(acetone-d6, δ, ppm): 60.0 (CH2O), 58.5 (CH2O), 55.1 (CH2O), 51.0 (CH2N), 47.6 (CH2N), 39.2 (B-OCH2), -457.3 (C-carborane), -486.3 (C-carborane).

11

B NMR

(acetone-d6, δ, ppm): 116.5, 102.4, 22.4, 20.3, -0.9, -4.1, -34.1, -38.8, -384.4, -411.1, 443.7, -499.3. IR-FT (nujol, ν, cm-1): 2534 (BH). HRESIMS: found 496.4062; C12H38NB18FeO3+H requires 496.4067. Reactions of 2-4 with tertiary alkylamines, general procedure. Synthesis of 11-16. To a solution of 1 mmol of 2-4 in 15 mL of abs. acetonitrile 2 mmol of appropriate amine was added and the mixture was stirred at the room temperature for 3 min (3) or refluxed for 10 min (2, 4). Then the volatiles were removed in vacuum and products were purified by silica gel column chromatography eluting with CH2Cl2.

21



2.78. C13H40NB18FeO2 requires (%): C, 31.68; H, 8.18; N, 2.84. 1H NMR (acetone-d6, δ,

Dalton Transactions


DOI: 10.1039/C4DT03015J

8-(4-(2-Hydroxyethyldimethylammonium)butoxy)-1,1’,2,2’-tetracarba-3-commoferra-closo-tricosaborate (11). Prepared from 50 mg (0.12 mmol) of 3 and 0.025 mL (0.23 mmol) of 2-(dimethylamino)ethanol. Yield 40 mg (98%) as a brown foam. Found

2.91. 1H NMR (acetone-d6, δ, ppm): 63.22 (br. s, 2H, CH-carborane), 35.62 (br. s, 2H, CH-carborane).

13

C NMR (acetone-d6, δ, ppm): 62.2 (CH2OH), 57.8 (CH2N), 53.6

(CH2N), 48.1 (CH3N), 11.7 (CH2), 9.0 (CH2O), 7.1 (CH2), -479.1 (C-carborane), -516.5 (C-carborane). 11B NMR (acetone-d6, δ, ppm): 117.8, 99.6, 35.6, 24.8, -1.9, -7.2, -38.5, 373.2, -389.3, -446.9, -494.1. IR-FT (nujol, ν, cm-1): 3294 (OH), 2531 (BH). HRESIMS: found 480.4129; C12H40NB18FeO2-H requires 480.4118. 8-(5-(2-Hydroxyethyldimethylammonium)pentoxy)-1,1’,2,2’-tetracarba-3-commoferra-closo-tricosaborate (12). Prepared from 100 mg (0.24 mmol) of 4 and 0.05 mL (0.50 mmol) of 2-(dimethylamino)ethanol. Yield 100 mg (83%) as a brown solid. Found (%): C, 31.33; H, 8.57; N, 2.71. C13H42NB18FeO2 requires (%): C, 31.55; H, 8.55; N, 2.83. 1H NMR (acetone-d6, δ, ppm): 65.44 (br. s, 2H, CH-carborane), 31.53 (br. s, 2H, CH-carborane).

13

C NMR (acetone-d6, δ, ppm): 63.5 (CH2OH), 61.1 (CH2N), 54.4

(CH2N), 49.4 (CH3N), 15.1 (CH2), 14.3 (CH2), 10.8 (CH2OB), 10.4 (CH2), -493.9 (Ccarborane), -535.5 (C-carborane).

11


27.8, -1.85, -6.6, -39.5, -368.1, -378.0, -446.1, 483.8. IR-FT (nujol, ν, cm-1): 3288 (OH), 2524 (BH). HRESIMS: found 494.4275; C13H42NB18FeO2-H requires 494.4322. 8-(2-(2-(2-Hydroxyethyl-dimethylammonium)ethoxy)ethoxy)-1,1’,2,2’-tetracarba-3commo-ferra-closo-tricosaborate (13). Prepared from 100 mg (0.24 mmol) of 2 and 0.05 mL (0.5 mmol) of 2-(dimethylamino)ethanol. Yield 110 mg (92%) as a brown foam. Found (%): C, 28.78; H, 8.02; N, 2.70. C12H40NB18FeO3 requires (%): C, 29.01; H, 8.11; N, 2.82. 1H NMR (acetone-d6, δ, ppm): 69.00 (br. s, 2H, CH-carborane), 35.53 (br. s, 2H, CH-carborane).

13

C NMR (acetone-d6, δ, ppm): 62.4 (CH2OH), 59.1 (CH2N), 55.7 22



(%): C, 29.75; H, 8.33; N, 2.94. C12H40NB18FeO2 requires (%): C, 29.97; H, 8.38; N,

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DOI: 10.1039/C4DT03015J

(CH2O), 55.7 (CH2N), 52.7 (CH2O), 48.2 (CH3N), 20.2 (CH2OB), -478.5 (C-carborane), 514.9 (C-carborane). 11B NMR (acetone-d6, δ, ppm): 117.6, 101.1, 31.4, 25.5, -1.5, -5.8, -37.9, -39.1, -374.6, -390.3, -441.3, -489.5. IR-FT (nujol, ν, cm-1): 3294 (OH), 2529

8-(4-(Prop-2-ynyldimethylammonium)butoxy)-1,1’,2,2’-tetracarba-3-commo-ferracloso-tricosaborate (14). Prepared from 30 mg (0.08 mmol) of 3 and 0.01 mL (0.1 mmol) of N,N-dimethylprop-2-yn-1-amine. Yield 30 mg (83%) as a brown foam. Found (%): C, 32.54; H, 8.01; N, 2.92. C13H38NB18FeO requires (%): C, 32.88; H, 8.07; N, 2.95. 1

H NMR (acetone-d6, δ, ppm): 64.10 (br. s, 2H, CH-carborane), 35.86 (br. s, 2H, CH-

carborane).

13

C NMR (acetone-d6, δ, ppm): 79.8 (HC≡C-), 68.8 (HC≡C-), 56.7 (CH2N),

50.8 (CH2N), 46.9 (CH3N), 11.7 (CH2), 8.4 (CH2O), 7.2 (CH2). -480.9 (C-carborane), 517.2 (C-carborane). 11B NMR (acetone-d6, δ, ppm): 117.9, 99.7, 35.6, 24.8, -1.9, -7.2, 38.6, -373.6, -389.8, -446.9, -495.4. IR-FT (nujol, ν, cm-1): 2537 (BH), 2136 (C≡C). HRESIMS: found 474.4030; C13H38NB18FeO-H requires 474.4013. 8-(5-(Prop-2-ynyldimethylammonium)pentoxy)-1,1’,2,2’-tetracarba-3-commo-ferracloso-tricosaborate (15). Prepared from 100 mg (0.24 mmol) of 4 and 0.06 mL (0.56 mmol) of N,N-dimethylprop-2-yn-1-amine. Yield 90 mg (75%) as a brown foam. Found (%): C, 31.23; H, 8.17; N, 2.75. C14H40NB18FeO requires (%): C, 34.39; H, 8.25; N, 2.86. 1

H NMR (acetone-d6, δ, ppm): 65.45 (br. s, 2H, CH-carborane), 31.39 (br. s, 2H, CH-

carborane).

13

C NMR (acetone-d6, δ, ppm): 80.9 (HC≡C-), 69.9 (HC≡C-), 60.0 (CH2N),

52.3 (CH2N), 48.6 (CH3N), 15.3 (CH2), 14.3 (CH2), 10.3 (CH2), 9.9 (CH2O),. -491.4 (Ccarborane), -533.0 (C-carborane).

11


27.8, -1.85, -6.6, -39.5, -368.1, -378.0, -446.1, 483.8. IR-FT (nujol, ν, cm-1): 2548 (BH), 2133 (C≡C). HRESIMS: found 488.4211; C14H40NB18FeO-H requires 488.4170. HRESIMS: found 512.4144; C14H40NB18FeO+Na requires 512.4146.

23



(BH). HRESIMS: found 496.4099; C12H40NB18FeO3-H requires 496.4067.

Dalton Transactions


DOI: 10.1039/C4DT03015J

8-(2-(2-(2-Prop-2-ynyldimethylammonium)ethoxy)ethoxy)-1,1’,2,2’-tetracarba-3commo-ferra-closo-tricosaborate (16). Prepared from 100 mg (0.24 mmol) of 2 and 0.06 mL (0.56 mmol) of 2-(dimethylamino)ethanol. Yield 110 mg (92%) as a brown

7.80; N, 2.85. 1H NMR (acetone-d6, δ, ppm): 61.72 (br. s, 2H, CH-carborane), 36.45 (br. s, 2H, CH-carborane).

13

C NMR (acetone-d6, δ, ppm): 79.5 (HC≡C-), 68.0 (HC≡C-),

66.36 (CH2O), 58.0 (CH2N), 55.6 (CH2O), 50.7 (CH2N), 47.1 (CH3N), 18.2 (CH2O-B). 477.2 (C-carborane), -512.8 (C-carborane).

11

B NMR (acetone-d6, δ, ppm): 117.2,

101.1, 30.5, 25.0, -1.3, -5.7, -36.7, -38.8, -374.9, -392.2, -440.7, -489.8. IR-FT (nujol, ν, cm-1): 2542 (BH), 2131 (C≡C). HRESIMS: found 490.3990; C13H38NB18FeO2-H requires 490.3973. Synthesis of deoxyadenosine conjugates 18-20(general procedure). To a solution of 1 mmol of 2-4 in 25 mL of abs. acetonitrile 1.05-1.1 mmol of 8-(2dimethylaminoethyl)-amino-2’-deoxyadenosine (17) were added and the mixture was refluxed for 10 min (3) or 1 h (2, 4). The volatiles were removed in vacuum and products were purified by silica gel column chromatography eluting with CH3OH. 8-[4-(4-[(2-(2’-desoxyadenosine-8-yl-amino)-ethyl)(dimethyl)ammonio]butoxy)](H)1,1’,2,2’-tetracarba-3-commo-ferra-closo-tricosaborate (18). Prepared from Found (%): C, 35.97; H, 7.14; N, 13.38. C22H52N7B18FeO4 requires (%): C, 36.24; H, 7.19; N, 13.45. 1H NMR (acetone-d6, δ, ppm): 63.77 (br. s, 2H, CH-carborane), 37.79 (br. s, 2H, CH-carborane), 7.13 (s, 1H, H-2), 5.56 (br. s, 1H, OH-3’), 5.44 (br. s, 1H, OH5’), 4.39 (s, 2H, NH2-6).

13

C NMR (acetone-d6, δ, ppm): 151.3 (C-6), 149.1 (C-4), 148.7

(C-8), 148.4 (C-2), 115.8 (C-5), 87.0 (C-4’), 82.8 (H-1’), 71.3 (H-3’), 61.0 (C-5’), 59.0 (CH2N), 57.6 (CH2N), 48.0 (CH3N), 37.9 (C-2’), 34.5 (CH2N), 14.2 (CH2), 12.0 (CH2), 7.26 (CH2O), -470.5 (C-carborane), -508.2 (C-carborane).

11

B NMR (acetone-d6, δ,

ppm): 115.8, 100.6, 32.2, 23.6, -1.7, -6.8, -38.4, -375.9, -396.6, -448.5, -497.6. IR-FT 24



foam. Found (%): C, 31.41; H, 7.73; N, 2.79. C13H38NB18FeO2 requires (%): C, 31.81; H,

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DOI: 10.1039/C4DT03015J

(nujol, ν, cm-1): 3359 (OH, NH), 2537 (BH), 1639 (Ar). HRESIMS: found 730.5300; C22H52N7B18FeO4+H requires 730.5303. 8-[4-(5-[(2-(2’-desoxyadenosine-8-yl-amino)-ethyl)(dimethyl)ammonio]pentoxy)]-

mg (0.38 mmol) of 3 and 155 mg (0.46 mmol) of 17. Yield: 140 mg (50%) as a brown foam. Found (%): C, 36.79; H, 7.24; N, 13.12. C23H54N7B18FeO4 requires (%): C, 37.17; H, 7.32; N, 13.19. 1H NMR (acetone-d6, δ, ppm): 67.18 (br. s, 2H, CH-carborane), 33.14 (br. s, 2H, CH-carborane), 7.36 (s, 1H, H-2), 6.02 (br. s, 1H, OH-3’), 5.56 (br. s, 1H, OH5’), 4.71 (s, 2H, NH2-6).

13

C NMR (acetone-d6, δ, ppm): 151.6 (C-6), 149.5 (C-4), 148.8

(C-8), 148.6 (C-2), 116.1 (C-5), 87.1 (C-4’), 82.9 (H-1’), 71.4 (H-3’), 61.2 (C-5’), 60.7 (CH2N), 60.1 (CH2N), 49.3 (CH3N), 37.9 (C-2’), 35.3 (CH2N), 17.9 (CH2), 15.2 (CH2), 14.5 (CH2), 10.4 (CH2O), -483.6 (C-carborane), -524.7 (C-carborane).

11

B NMR

(acetone-d6, δ, ppm): 118.8, 101.4, 36.4, 27.3, -1.6, -6.2, -38.9, -371.1, -383.9, -448.0, 486.2. IR-FT (nujol, ν, cm-1): 3380 (OH, NH), 2533 (BH), 1636 (Ar). HRESIMS: found 744.5449; C23H54N7B18FeO4+H requires 744.5460. 8-[4-(2-{2-[(2-(2’-desoxyadenosine-8-yl-amino)ethyl)(dimethyl)ammonio]ethoxy}ethoxy)]-(H)1,1’,2,2’-tetracarba-3-commo-ferracloso-tricosaborate (20). Prepared from 108 mg (0.26 mmol) of 3 and 108 mg (0.32 mmol) of 17. Yield: 180 mg (92%) as a brown foam. Found (%): C, 35.18; H, 7.07; N, 13.09. C22H52N7B18FeO5 requires (%): C, 35.46; H, 7.03; N, 13.16. 1H NMR (acetone-d6, δ, ppm): 65.28 (br. s, 2H, CH-carborane), 37.40 (br. s, 2H, CH-carborane), 7.30 (s, 1H, H-2), 5.26 (br. s, 1H, OH-3’), 4.83 (s, 2H, NH2-6), 4.73 (br. s, 1H, OH-5’).

13

C NMR

(acetone-d6, δ, ppm): 151.6 (C-6), 148.9 (C-4), 148.7 (C-8), 148.5 (C-2), 116.0 (C-5), 86.5 (C-4’), 82.5 (H-1’), 70.9 (H-3’), 60.0 (C-5’), 59.7 (CH2N), 58.5 (CH2N), 56.3 (CH2O), 55.6 (CH2O), 49.2 (CH3N), 37.5 (C-2’), 34.0 (CH2N), 20.3 (CH2O), -484.1 (Ccarborane), -521.2 (C-carborane).

11

B NMR (acetone-d6, δ, ppm): 119.1, 102.4, 29.7, 25



(H)1,1’,2,2’-tetracarba-3-commo-ferra-closo-tricosaborate (19). Prepared from 155

Dalton Transactions


DOI: 10.1039/C4DT03015J

28.1, 24.6, -1.3, -5.7, -37.2, -39.7, -379.7, -400.0, -447.9, -497.8. IR-FT (nujol, ν, cm-1): 3379 (OH, NH), 2539 (BH), 1631 (Ar). HRESIMS: found 746.5242; C22H52N7B18FeO5+H requires 746.5252. of

2-4

with

bis(diphenylphosphino)ethane,

general

procedure.

Synthesis of 21-23. To a solution of 1 mmol of 2-4 in 20 mL of abs. mesitylene 3.1 mmol of bis(diphenylphosphino)ethane (dppe) was added and the mixture was heated at 80°C for 30 (3), 60 (4) or 120 min (2). Then the solution was cooled and then 100 mL of hexane was added and the mixture was stored at -20°C overnight. The precipitates were filtered and then purified by silica gel column chromatography eluting with CH2Cl2. 8-[4-(4-((2-(diphenylphosphino)ethyl)diphenylphosphonio)butoxy)]-(H)1,1’,2,2’tetracarba-3-commo-ferra-closo-tricosaborate (21) Prepared from 120 mg (0.30 mmol) of 3 and 360 mg (0.90 mmol) of dppe. Yield: 70 mg (30%) as a brown foam. M.p.110°C (dec.). Found (%): C, 51.29; H, 6.71. C34H53B18FeOP2 requires (%): C, 51.68; H, 6.76. 1H NMR (acetone-d6, δ, ppm): 64.45 (br. s, 2H, CH-carborane), 35.30 (br. s, 2H, CH-carborane), 7.08-6.31 (m, 20H, Ph).

13

C

NMR (acetone-d6, δ, ppm): 135.5 (d, PCipso(Ph), JC-P = 14 Hz), 133.5 (br.s, Ph), 131.7 (d, Ph, JC-P = 19 Hz), 130.2 (d, Ph, JC-P = 9 Hz), 128.5 (d, Ph, JC-P = 14 Hz), 128.3 (br.s, Ph), 128.0 (d, Ph, JC-P = 7 Hz), 114.5 (d, P+Cipso(Ph), JC-P = 83 Hz), 16.4 (d, CH2P, JC-P = 18 Hz), 15.9 (d, CH2CH2P+, JC-P = 15 Hz), 14.5 (dd, P+CH2CH2P, JC-P = 24 Hz, JC-P+ = 49 Hz), 11.7 (s, CH2O-B), 10.9 (d, CH2P+, JC-P = 50 Hz), 6.9 (s, CH2), -479.7 (C-carborane), -516.7 (C-carborane).

11

B NMR (acetone-d6, δ, ppm): 118.0, 101.0, 35.0, 25.5, -1.52, -

6.7, -39.0, -375.5, -390.4, -447.8, -494.3. 31P NMR (acetone-d6, δ, ppm): 23.5 (d, P+Ph2, JP-P = 47 Hz), -13.0 (d, CH2PPh2, JP-P = 47 Hz). IR-FT (nujol, ν, cm-1): 2531 (BH), 1591 (Ar). HRESIMS: found 791.4782; C34H53B18FeOP2+H requires 791.4801.

26



Reactions

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8-[4-(4-((2-(diphenylphosphino)ethyl)diphenylphosphonio)pentoxy)]-(H)1,1’,2,2’tetracarba-3-commo-ferra-closo-tricosaborate (22) Prepared from 120 mg (0.29 mmol) of 3 and 360 mg (0.90 mmol) of dppe. Yield: 220

C35H55B18FeOP2 requires (%): C, 52.27; H, 6.89. 1H NMR (acetone-d6, δ, ppm): 65.27 (br. s, 2H, CH-carborane), 30.91 (br. s, 2H, CH-carborane), 7.28-6.23 (m, 20H, Ph).

13

C

NMR (acetone-d6, δ, ppm): 135.9 (d, PCipso(Ph), JC-P = 13 Hz), 134.1 (br.s, Ph), 132.0 (d, Ph, JC-P = 19 Hz), 131.6 (d, Ph, JC-P = 10 Hz), 129.2 (d, Ph, JC-P = 12 Hz), 128.5 (br.s, Ph), 128.3 (br.s, Ph), 116.2 (d, P+Cipso(Ph), JC-P = 83 Hz), 20.3 (s, CH2), 17.5 (d, CH2P, JC-P = 18 Hz), 15.4 (dd, P+CH2CH2P, JC-P = 23 Hz, JC-P+ = 49 Hz), 14.9 (d, CH2P+, JC-P = 50 Hz), 14.4 (s, CH2),14.1 (d, CH2CH2P+, JC-P = 15 Hz), 9.6 (br.s, CH2O-B), -494.7 (C-carborane), -537.9 (C-carborane). 11B NMR (acetone-d6, δ, ppm): 119.0, 100.9, 39.8, 28.6, -1.6, -6.4, -39.5, -368.3, -376.5, -446.2, -483.0.

31

P NMR (acetone-d6, δ, ppm):

25.3 (d, P+Ph2, JP-P = 48 Hz), -11.1 (d, CH2PPh2, JP-P = 48 Hz). IR-FT (nujol, ν, cm-1): 2534 (BH), 1587 (Ar). HRESIMS: found 805.4960; C35H55B18FeOP2+H requires 805.4952. 8-[4-(2-(2-((2-(diphenylphosphino)ethyl)diphenylphosphonio)ethoxy)ethoxy)](H)1,1’,2,2’-tetracarba-3-commo-ferra-closo-tricosaborate (23) Prepared from 100 mg (0.25 mmol) of 3 and 300 mg (0.75 mmol) of dppe. Yield: 100 mg (50%) as a brown foam. Found (%): C, 50.31; H, 6.57. C34H53B18FeO2P2 requires (%): C, 50.65; H, 6.63. 1H NMR (acetone-d6, δ, ppm): 66.74 (br. s, 2H, CH-carborane), 35.12 (br. s, 2H, CH-carborane), 6.83-5.64 (m, 20H, Ph).

13

C NMR (acetone-d6, δ,

ppm): 135.4 (d, PCipso(Ph), JC-P = 14 Hz), 133.1 (br.s, Ph), 131.5 (d, Ph, JC-P = 19 Hz), 130.3 (d, Ph, JC-P = 9 Hz), 128.5 (br.s, Ph), 128.1 (br.s., Ph), 127.9 (br.s., Ph), 115.1 (d, P+Cipso(Ph), JC-P = 83 Hz), 57.1 (OCH2), 55.3 (br.s, OCH2CH2P+), 22.7 (s, CH2O-B), 17.1 (d, CH2P+, JC-P = 52 Hz), 16.3 (d, CH2P, JC-P = 18 Hz), 15.5 (dd, P+CH2CH2P, JC-P = 23 27



mg (92%) as a brown foam. M.p. 154-155°C. Found (%): C, 51.82; H, 6.84.

Dalton Transactions


DOI: 10.1039/C4DT03015J

Hz, JC-P+ = 48 Hz), -481.9 (C-carborane), -523.7 (C-carborane). 11B NMR (acetone-d6, δ, ppm): 117.9, 101.3, 31.6, 27.1, -1.03, -5.4, -36.5, -38.9, -369.2, -382.5, -436.4, -478.4. 31

P NMR (acetone-d6, δ, ppm): 25.3 (d, P+Ph2, JP-P = 48 Hz), -11.1 (d, CH2PPh2, JP-P =

C34H53B18FeO2P2+H requires 807.4750. 8-iodo-8’-(4-(((H)1,1’,2,2’-tetracarba-3-commo-ferra-closo-tricosaborate)-8yl)oxybutyl)(2-(methyldiphenylphosphonio)ethyl)diphenylphosphonium)(H)1,1’,2,2’-tetracarba-3-commo-cobalta-closo-tricosaborate (25) Mixture of 100 mg (0.12 mmol) of 22 and of 50 mg (0.11 mmol) of 24 in methylene was hearted at the 80 °C for 6 h. Then the solution was cooled and then 100 mL of hexane was added and the mixture was stored at -20°C overnight. The precipitates were filtered and then purified by silica gel column chromatography eluting with CH2Cl2. Yield 50 mg (36%) as a brown foam. Found (%): C, 37.07; H, 6.00. C39H75B36FeCoIOP2 requires (%): C, 37.39; H, 6.03. 1H NMR (acetone-d6, δ, ppm): 65.59 (br. s, 2H, CH-carborane), 30.95 (br. s, 2H, CH-carborane), 7.57-6.30 (m, 20H, Ph), 4.53 (s, 2H, CH-carborane), 3.60 (s, 2H, CH-carborane).

13

C NMR (acetone-d6, δ, ppm): 136.0 (d, Ph, JC-P = 14 Hz),

134.1 (dd, P+Cipso(Ph), JC-P = 82 Hz, J = 3 Hz), 134.0 (d, Ph, JC-P = 9 Hz), 132.0 (d, Ph, JC-P = 19 Hz), 131.7 (d, Ph, JC-P = 10 Hz), 131.5 (d, Ph, JC-P = 10 Hz), 129.8 (d, Ph, JC-P = 11 Hz), 129.3 (d, Ph, JC-P = 12 Hz), 129.1 (s, Ph), 129.0 (s, Ph), 128.9 (s, Ph), 128.3 (d, Ph, JC-P = 6 Hz), 119.1 (d, P+Cipso(Ph), JC-P = 67 Hz), 116.1 (d, P+Cipso(Ph), JC-P = 83 Hz), 114.6 (d, P+Cipso(Ph), JC-P = 84 Hz), 58.4 (s, C-carborane), 50.3 (s, C-carborane), 22.4 (s, CH2), 21.1 (d, CH2P+, JC-P = 43 Hz), 17.5 (d, CH2, JC-P = 19 Hz), 15.4 (m, P+CH2), 14.7 (d, CH2P+, JC-P = 49 Hz), 14.1 (s, CH2), 9.9 (br.s, CH2O-B), -492.2 (Ccarborane), -532.2 (C-carborane).

11


28.7, 3.1, -1.8, -3.7, -6.4, -15.2, -22.9, -39.5, -368.1, -376.6, -446.8, -483.4.

31

P NMR

28



48 Hz). IR-FT (nujol, ν, cm-1): 2532 (BH), 1595 (Ar). HRESIMS: found 807.4698;

Page 29 of 72


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(acetone-d6, δ, ppm): 25.3 (d, P+Ph2, JP-P = 44 Hz), 7.2-2.9 (m, B-P+). HRESIMS: found 1253.6685; C39H75B36FeCoIOP2+H requires 1253.6722. Crystallography

3

8

9

21

C8H29B18FeO

C12H38B18FeNO2

C14H44B18Cl2FeNO3

C35.50H56B18Cl3FeOP2

391.74

478.86

595.83

917.52

120

120

120

120

Monoclinic

Triclinic

Monoclinic

Triclinic

Pc

P-1

P21/c

P-1

4 (2)

6 (3)

4 (1)

2 (1)

a, Å

16.938(3)

10.4813(8)

13.3551(4)

12.2119(4)

b, Å

6.9590(11)

16.4726(13)

18.8652(6)

13.9471(5)

c, Å

23.000(3)

23.1236(19)

12.7661(4)

15.1730(5)

α, °

90.00

71.221(2)

90.00

72.620(2)

β, °

131.788(8)

85.257(2)

106.6490(10)

81.392(2)

90.00

83.086(2)

90.00

69.815(2)

2021.4(5)

3748.3(5)

3081.54(17)

2311.68(14)

Formula M T, K Crystal system Space group Z (Z’)

γ, ° V, Å

3

dcalc, g·cm-3

1.287

1.273

1.284

1.318

-1

7.42

6.17

6.84

50.84

F(000)

804

1494

1236

948

2θmax, °

57

56

58

130

Reflns collected

9666

41773

37992

25676

Independent reflns

9666

18049

8206

7547

Reflns with I>2σ(I)

7814

9011

6512

6335

Parameters

506

931

321

680

R1

0.0598

0.0563

0.0385

0.0453

wR2

0.1535

0.1114

0.1065

0.1341

GOF Residual electron density, e·Å-3 (dmin/dmax )

1.016

0.911

1.008

1.048

0.858/-1.009

0.585/-0.659

0.453/-0.423

0.443/-0.745

µ, cm

X-ray diffraction investigations of 3, 8, 9 and 21 were carried out using Bruker Apex II Duo diffractometer (MoKα-radiation, ω-scans for 3, 8 and 9; CuKα-radiation, ω- and φ29



Table 1. Crystallographic data and refinement parameters for 3, 8, 9 and 21.

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DOI: 10.1039/C4DT03015J

scans for 21). All structures were solved by direct method and refined by least-squares method against F2hkl using anisotropic full-matrix approximation. Positions of H(C) and H(B) hydrogen atoms were calculated with the only exception of hydrogen atoms of

as well as those of H(O) and H(N) hydrogen atoms in structures 8 and 9. All hydrogen atoms were refined in isotropic approximation. General crystallographic data and parameters of refinements are listed in Tables 1. All calculations were carried out using SHELXTL PLUS software27.

30



carborane cages in 21, positions of which were found from difference Fourier synthesis

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Notes and references a

A.N.Nesmeyanov Institute of Organoelement Compounds, Russian Academy of

b

College of Materials Science and Engineering, Beijing University of Chemical

Technology, 100029, Beijing, China. c

Laboratory of Molecular Virology and Biological Chemistry, Institute of Medical Biology,

Polish Academy of Sciences, 106 Lodowa St., 93-232 Lodz, Poland.

†In memory of Professor Kenneth Wade. ‡ See Supporting Information the

1

H,

13

C,

11

B and

31

P NMR spectra. Electronic

supplementary information (ESI) available: structural data, features of structure solution and refinement. CCDC 1025613-1025616. For ESI and crystallographic data in CIF or other electronic format see DOI: 1

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8-Tetrahydrofuronium and 8-tetrahydropyronium derivatives of iron bis(dicarbollide)(-I)



were synthesized and their reactivity towards various nucleophiles was studied.



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Compound 4.




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Compound 5



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Compound 7



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Compound 8



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Compound 10



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Compound 12



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Compound 14



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Compound 16



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Compound 19



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Compound 20



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Compound 21



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Compound 22



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