N-arylammonio- and N-pyridinium-substituted derivatives of dodecahydro-closo-dodecaborate(2-)

We report two methods for preparing N-arylammonio, N-pyridyl and N-arylamino dodecaborates: heating of the tetrabutylammonium salt of dodecahydro-closo-dodecaborate(2-) with aryl and pyridyl amines, or nucleophilic attack of [closo-B₁₂H₁₁NH₂]²⁻ on a strongly deactivated aromatic system. With aryl amines we obtained [1-closo-B₁₂H₁₁N(R¹)₂C₆H₅]⁻ (R¹ = H, CH₃). With 4-(dimethylamino)pyridine, [1-closo-(B₁₂H₁₁NC₅H₄)-4-N(CH₃)₂]⁻, with a bond between the boron and the pyridinium nitrogen, was obtained. A presumable mechanism for this kind of reactions is reported. By nucleophilic substitution, two products, [1-closo-(B₁₂H₁₁NHC₆H₃)-3,4-(CN)₂]²⁻ and [1-closo-(B₁₂H₁₁NHC₆H₂)-2-(NO₂)-4,5-(CN)₂]²⁻, were formed with 4-nitrophthalonitrile and 1-chloro-2,4-dinitrobenzene gave [1-closo-(B₁₂H₁₁NHC₆H₃)-2,4-(NO₂)₂]²⁻. For [1-closo-B₁₂H₁₁N(CH₃)₂C₆H₅]⁻ and [1-closo-(B₁₂H₁₁NHC₆H₃)-2,4-(NO₂)₂]²⁻ single crystal X-ray structures were obtained.     

Synthesis and X-ray structural characterization of the triphenylphosphine derivative of the closo-dodecaborate anion, closo-[B12H11P(C6H5)3][N(n-C4H9)4]

The reaction of a molar excess of closo-[B₁₂H₁₁I][N(n-C₄H₉)₄]₂ (1) with tetrakis(triphenylphosphine)palladium (0), Pd(0)L₄, yields to the formation of the title monoanionic compound, closo-[1-B₁₂H₁₁P(C₆H₅)₃][N(n-C₄H₉)₄] (2). The structure of 2 was determined by X-ray diffraction analysis performed on a single crystal. The mechanism of formation of 2 is also discussed. We suggested a two-step mechanism for the formation of 2 consisting in a oxidative addition of the palladium complex followed by a reductive elimination involving P(C₆H₅)₃ and assisted by Na₂CO₃. To our knowledge, this is the first example of monosubstitution of B₁₂ with formation of boron-phosphorus bond.     

Synthesis of boron-containing tyrosine derivatives based on the closo-decaborate and closo-dodecaborate anions

A series of new boron-containing tyrosine derivatives [B _n H _n?1O(CH₂)₄O-4-C₆H₄CH₂CH-(NH₃)COOH]^? and [B _n H _n?1O(CH₂CH₂)₂O-4-C₆H₄CH₂CH(NH₃)COOH]^? (n = 10, 12) were prepared by ring opening of the cyclic oxonium derivatives of the decahydro-closo-decaborate and dodecahydro-closo-dodecaborate anions, respectively, with ethyl N-trifluoroacetyl-L-tyrosinate.     

Thermal conversions of chitosanium dodecahydro-<Emphasis Type="Italic">closo</Emphasis>-dodecaborate

The thermal behavior of chitosanium dodecahydro-closo-dodecaborate, (C₆O₄H₉NH₃)₂B₁₂H₁₂, was studied by thermal analysis, X-ray diffraction, and IR and X-ray photoelectron spectroscopy. As this compound is heated at a rate above 10–20 K/min, it ignites at a temperature of about 300°C. As the compound is heated to 1000°C at a rate below 10 K/min in an inert atmosphere, it yields a mixture of carbon and amorphous boron and/or boron carbides. The presence of a small amount of boron oxide in the product is explained by the formation of a partially oxidized hydroborate anion at the early stages of (C₆O₄H₉NH₃)₂B₁₂H₁₂ decomposition via the interaction between oxygen of the chitosanium cation and the B₁₂H₁₂²⁻ anion. Heating the initial compound in air at a rate below 10 K/min yields carbon and boron oxide as the main products. Molten boron oxide protects boron and/or boron carbides and boron nitride forming in small amounts in the particle bulk from oxidation.     

The synthesis of functional derivatives of the [1-CB9H10] anion by Brellochs reaction

Reactions of decaborane with various aldehydes in alkaline media were studied. The reactions with HCOH and 2-MeOC₆H₄CHO give the corresponding arachno-carboranes [6-R-arachno-CB₉H₁₃]⁻ (R = H, C₆H₄-2-OMe), whereas the reactions with C₆H₅CHO, 4-BrC₆H₄CHO, 4-MeCONHC₆H₄CHO, and 2-SC₄H₃CHO result in the nido-carboranes [6-R-nido-CB₉H₁₁]⁻ (R = C₆H₅, C₆H₄-4-Br, C₆H₄-4-NHCOMe, 2-SC₄H₃). Both the arachno- and nido-carboranes can be easily oxidized with elemental iodine in an alkaline aqueous solution giving the corresponding closo-derivatives [2-R-closo-2-CB₉H₉]⁻. These closo-2-isomers, under heating in solution, undergo rearrangement to more thermodynamically favorable closo-1-isomers [1-R-closo-1-CB₉H₉]⁻. The structure of (Bu₄N)[1-(4-BrC₆H₄)-1-CB₉H₉] was determined using single crystal X-ray diffraction.     

Facile formation of exo-nido→closo-rearrangement products upon the replacement of PPh3 ligands with bis(diphenylphosphino)alkanes in “three-bridge” ruthenacarborane 5,6,10-[RuCl(PPh3)2]-5,6,10-(μ-H)3-10-H-exo-nido-7,8-C2B9H8

The replacement of the PPh₃ ligands in “three-bridge” exo-nido-ruthenacarborane 5,6,10-[RuCl(PPh₃)₂]-5,6,10-(μ-H)₃-10-H-exo-nido-7,8-C₂B₉H₈ with diphosphines, viz., 1,3-bis(diphenylphosphino)propane (dppp) or 1,4-bis(diphenylphosphino)butane (dppb) dramatically decreases the barrier to the thermal exo-nido→closo rearrangement affording the chelate closo-complexes 3,3-[Ph₂P(CH₂)_nPPh₂]-3-H-3-Cl-closo-3,1,2-RuC₂B₉H₁₁ (n = 3 or 4) under mild conditions. In the reaction with dppp, the rearrangement is accompanied by the formation of 17-electron paramagnetic closo-ruthenacarborane 3,3-[Ph₂P(CH₂)₃PPh₂]-3-Cl-closo-3,1,2-RuC₂B₉H₁₁, which could be isolated as the main product when the reaction was carried out at 80 °C. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2455–2459, November, 2005.     

Practical synthesis of 1,4-dioxane derivative of the closo-dodecaborate anion and its ring opening with acetylenic alkoxides

Practical method of synthesis of the 1,4-dioxane derivative of the closo-dodecaborate anion was developed. The cleavage of the dioxonium ring in [B₁₂H₁₁O(CH₂CH₂)₂O]⁻ with acetylenic alcohols gave rise to the preparation of closo-dodecaborate derivatives with terminal acetylene group. These compounds can be introduced into click reactions with phenylazide leading to the corresponding triazoles. The structures of (Bu₄N)[B₁₂H₁₁O(CH₂CH₂)₂O] and (Bu₄N)₂[B₁₂H₁₁(OCH₂CH₂)₂OCH₂CCH] · 0.5HOCH₂CCH were determined by single-crystal X-ray diffraction.     

Hexamethylenetetrammonium dodecahydro-<Emphasis Type="Italic">closo</Emphasis>-dodecaborate: Synthesis and study

The reaction of dodecahydro-closo-dodecaboric acid with hexamethylenetetramine (urotropin) was studied by potentiometric titration, chemical and X-ray diffraction analyses, thermogravimetry, and IR and X-ray photoelectron spectroscopy. The donor-acceptor bond with acid H⁺ cations involves only one of the nitrogen donor atoms of hexamethylenetetramine. The product (C₆H₁₂N₄H)₂B₁₂H₁₂ is isolated as a finely crystalline, easily filterable, and poorly soluble precipitate. A saturated solution of the product contains no more than 0.4 g of the salt per 100 g.     

Cage complexes as a molecular scaffold for polyfunctional and polytopic systems: Synthesis of the first closo-borate iron(II) clathrochelate

The ribbed functionalization of the clathrochelate iron(II) tris-dioximates as a potential “molecular scaffold” for the synthesis of polyfunctional and polytopic complexes with closo-dodecaborate-anion substituents was performed. closo-Dodecaborate-substituted clathrochelate [FeBd₂(Cl(B₁₂H₁₁NH)Gm)(BF)₂]^2? (where Bd^2? is α-benzyldioxime dianion, Gm is glyoxime residue) dianion was prepared starting from dichloride clathrochelate FeBd₂(Cl₂Gm)(BF)₂ precursor with amino-closo-dodecaborate (NBu₄)[B₁₂H₁₁NH₃] in the presence of potassium tert-amylate. This clathrochelate dianion was isolated as a tetra-n-butylammonium salt and characterized using elemental analysis, MALDI-TOF and PD mass, IR, UV-Vis, ⁵⁷Fe Mössbauer spectra as well as by ¹H, ¹¹B and ¹³C{¹H} NMR spectra.     

Structure and stability of closo-hexaboranes and their heteroanalogs

The molecular and electronic structures of closo-hexaboranes B₆H₆ ^2–, B₆H₇ ^–, and B₆H₈ and closo-heterohexaboranes XYB₄H₄ (X = Y = CH, N; X = BH, Y = CH^–, N^–, NH, O) were studed by the ab initio (MP2(full)/6-311+G**) and density functional (B3LYP/6-311+G**) methods. The bridging H atoms in closo-hexaboranes B₆H₇ ^– and B₆H₈ can undergo facile low-barrier migrations around the boron cage (the barrier heights are about 10—15 kcal mol^–1). All heteroboranes having octahedron-like structures with hypercoordinated N and O atoms are rather stable and can be the subject of synthetic research efforts.     

Synthesis of 12-vertex mixed ligand closo-cobaltacarborane complexes and molecular structure of [3,3-(Ph2P(CH2)2PPh2)-3-Cl-closo-3,1,2-CoC2B9H11]

A reaction of complexes CoCl₂(dppe) (dppe is the 1,2-bis(diphenylphosphino)ethane) or CoCl₂(dppp) (dppp is the 1,3-bis(diphenylphosphino)propane) with [K][7,8-nido-C₂B₉H₁₂] upon reflux in benzene led to the mixed ligand closo-cobaltacarboranes [3,3-(Ph₂P(CH₂) _n PPh₂)-3-Cl-closo-3,1,2-Co^IIIC₂B₉H₁₁] (n = 2 and 3, respectively) in moderate yields (34 and 16%). The structure of the 18-electron complexes in solution and the solid state was studied by NMR and IR spectroscopy, the structure in the case of the closo-complex with dppe-ligand was confirmed by X-ray crystallography.     

Dodecahydro-<Emphasis Type="Italic">closo</Emphasis>-dodecaborate anion intercalation into graphite oxide

It is demonstrated by X-ray diffraction that, in the case of dodecahydro-closo-dodecaborates with small cations (H⁺, Li⁺, Na⁺, K⁺, NH ₄ ⁺ ), the intercalation of the B₁₂H ₁₂ ^2? anion into the interlayer space of graphite oxide is more favorable than the crystallization of a free salt. In the case of large cations commensurable with B₁₂H ₁₂ ^2? (e.g., Cs⁺), no intercalation takes place because these cations and the dodecaborate-closo-dodecaborate anion form stable cubic crystals as a separate phase outside the graphite oxide structure.     

Synthesis and configurational assignment of diastereomers ofcloso-3,3-[η2,3-(2-methylenebicyclo[2.2.1]hepta-2,5-dien-2-yl)]-1-benzyl-3,1,2-dicarbollylrhodium complexes

The previously synthesized mixture of diastereomeric complexescloso-3,3-(η^2,3-C₇H₇CH₂)-1-(PhCH₂)-3,1,2-RhC₂B₉H₁₀ was separated by TLC on silica gel into individual diastereomers, whose stereochemistry and relative configurations were determined by X-ray diffraction analysis. Triplet- and quadruplet-like signals are marked with an asterisk Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2069–2070, November, 1997.     

Ethynylmonocarba-closo-dodecaborates: M[12-HCC-closo-1-CB11H11] and M[7,12-(HCC)2-closo-1-CB11H10] (M = Cs, [Et4N])

Cesium and tetraethylammonium salts of the ethynyl functionalized monocarba-closo-dodecaborate anions [12-HCC-closo-1-CB₁₁H₁₁]⁻ and [7,12-(HCC)₂-closo-1-CB₁₁H₁₀]⁻ were obtained by desilylation of [Et₄N][12-Me₃SiCC-closo-1-CB₁₁H₁₁] and [Et₄N][7,12-(Me₃SiCC)₂-closo-1-CB₁₁H₁₀], respectively. Their thermal properties were examined by differential scanning calorimetry. The compounds were characterized by multi-NMR, IR, and Raman spectroscopy, (−)-MALDI mass spectrometry, and elemental analysis. Single-crystals of Cs[12-HCC-closo-1-CB₁₁H₁₁] and [Et₄N][7,12-(HCC)₂-closo-1-CB₁₁H₁₀] were studied by X-ray diffraction. The discussion of the spectroscopic and structural properties is supported by data derived from theoretical calculations using density functional theory as well as perturbation theory.     

Synthesis and NMR spectra of the hydroxyundecahydro-closo-dodecaborate [B12H11OH]2− and its acylated derivatives

Tetrabutylammonium hydroxyundecahydro-closo-dodecaborate was obtained in high yield via [B₁₂H₁₁NMP]^–(NMP =N-methylpyrrolidone) by the modified method. [B_i2H₁₁OH]^2– is easily acylated by aromatic acyl chlorides to give novel compounds [B₁₂H₁₁OCOAr]^2– in high yields. All the compounds were characterized by standard and special NMR methods.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 722–725, March, 1996.     

Probing the structure, stability and hydrogen storage properties of calcium dodecahydro-closo-dodecaborate

Calcium borohydride can reversibly store up to 9.6 wt% hydrogen; however, the material displays poor cyclability, generally associated with the formation of stable intermediate species. In an effort to understand the role of such intermediates on the hydrogen storage properties of Ca(BH₄)₂, calcium dodecahydro-closo-dodecaborate was isolated and characterized by diffraction and spectroscopic techniques. The crystal structure of CaB₁₂H₁₂ was determined from powder XRD data and confirmed by DFT and neutron vibrational spectroscopy studies. Attempts to dehydrogenate/hydrogenate mixtures of CaB₁₂H₁₂ and CaH₂ were made under conditions known to favor partial reversibility in calcium borohydride. However, up to 670 K no notable formation of Ca(BH₄)₂ (during hydrogenation) or CaB₆ (during dehydrogenation) occurred. It was demonstrated that the stability of CaB₁₂H₁₂ can be significantly altered using CaH₂ as a destabilizing agent to favor the hydrogen release.     

Synthesis of Schiff bases and benzylamino derivatives containing [1-B<Subscript>10</Subscript>H<Subscript>9</Subscript>NH<Subscript>3</Subscript>]<Superscript>−</Superscript> anion

Reactions of an amino derivative of the closo-decaborate anion [1-B₁₀H₉NH₃]^– with aromatic aldehydes afforded Schiff bases [1-B₁₀H₉NH=CHAr]^– (Ar=Ph, C₆H₄-2-OMe, or C₆H₄-4-NHCOMe). The reduction of the latter with sodium borohydride gave the corresponding benzylamino derivatives [1-B₁₀H₉NH₂CH₂Ar]^–.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2004–2007, September, 2004.     

Separation of racemiccloso-3,3-(η3,2-norbornadienyl)rhodacarboranes into enantiomers by HPLC on chiral stationary phasesinto enantiomers by HPLC on chiral stationary phases

Racemiccloso-rhodacarboranes,vis. closo-(η^3,2-C₇H₃-2-CR ₂ ¹ )-1-R²-2-R³-3,1,2-RhC₂B₉H₉ (R¹=R²=R³=H; R¹=H, R²=R³=Me; R¹=R²=R³=Me) and (closo-2,2-(η^3,2-C₇H₇-2-CH₂)-2,1,7-RhC₂B₉H₁₁), were successfully separated into enantiomers by high-performance liquid chromatography (HPLC). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 759–761, April, 2000.     

B-frame supported bimetallics. [(PMe2ph)2PtB9H11Ru(η-PrC6H4Me)] and [(PMe2ph)2PtB9H9Ru(η-PrC6H4Me)]; an interesting pair of electron-deficient nido and closo geometries

[7,7-(PMe₂Ph)₂-9-(η⁶-^isoPrC₆H₄Me)-7,9-PtRuB₉H₁₁] has a formal closo Wadian cluster-electron count, but a nido geometry, whereas [1-(η⁶-^isoPrC₆H₄Me)-4,4-(PMe₂Ph)₂-1-4-RuPtB₉H₉], which does have a closo geometry, has a formal sub-closo cluster electron count; both compounds are formed in the reaction between [6-(η⁶-^isoPrC₆H₄Me)-nido-6 RuB₉H₁₃], KH and [PtCl₂(PMe₂Ph)₂].     

A convenient approach towards boron cluster modifications with adenosine and 2′-deoxyadenosine

New 2′-deoxyadenosine and adenosoine modifications: 8-[(2-dimethylaminoethyl)amino]-2′-deoxyadenosine and 8-[(2-dimethylaminoethyl)amino]adenosine were prepared and their reactivity towards cyclic oxonium adducts of closo-dodecaborate and cobalt-bis-dicarbollide was studied. The cleavage reactions of clusters oxonium rings by N,N-dimethylanio group of modified nucleosides led to the first [B₁₂H₁₂]²⁻ and new [Co(C₂B₉H₁₁)₂]⁻ conjugates with adenosine and 2′-deoxyadenosine respectively. The proposed methodology provides a convenient route for the synthesis of libraries of boron cluster modified adenosine and 2′-deoxyadenosine derivatives for biological screening.