V. V. Avdeeva

Specific interactions in metal salts and complexes with cluster boron anions BnHn2− (n = 6, 10, 12)

Specific interactions that appear in metal salts and complexes with cluster boron anions BnHn2− (n = 6, 10, 12) have been discussed. These interactions, as well as chemical bonds, involve vertices, edges, or faces of boron polyhedra. Specific interactions have a considerable effect on the structure of compounds, making a significant contribution to the formation of the unit cell and forming supramolecular assemblies. Compounds containing BnHn2− cluster anions shed new light onto the nature of specific interactions owing to their many-center character and great variety.

Coordination compounds of electron-deficient boron cluster anions BnHn2− (n = 6, 10, 12)

This survey concerns the coordination ability of BnHn2− (n = 6, 10, 12) boron cluster anions and their derivatives in complex formation. Boron cluster anions form four types of compounds: salts of organic cations and alkali-metal cations, including Cat2BnHn, where specific interactions can be observed between a cation Cat and a boron cluster anion; salts of protonated anions CatB6H7 and CatB10H11, analogues of Cat[MBnHn] complexes, where an extra hydrogen atom appears bound with the BBB face of a boron polyhedron and performs as a hard acceptor; metal complexes with outer-sphere boron cluster anions where specific ligand-ligand interactions may be observed between a boron cluster anion and an inner-sphere ligand; and true metal complexes with boron cluster anions that enter the inner coordination sphere. The last case characterizes closo-hydroborate anions as polydentate ligands whose denticity can vary widely under the effect of substituents or other ligands in the complex.

Redox, complexation, and substitution reactions in [Cu2B10H10]-2,2′-bipyridylamine-CH3CN system

Reaction of [Cu2B10H10] with 2,2′-bipyridylamine (bpa) in acetonitrile was studied. A redox reaction was found to proceed in reaction solution at ambient temperature. Copper coordination compounds with the metal of different oxidation states—[Cu2I(bpa)2B10H10] · 2NCCH3, [Cu4II(bpa)4(OH)4][Cu2I(B10H10)3] · nNCCH3, [CuII(bpa)2(NCCH3)2](2-B10H9bpa)2 · 2H2O, [Cu2II(bpa)2(OH)2B10H10], and [(Cu2II(bpa)2(CO3)2] · H2O—were isolated under various reaction conditions. The compounds were characterized by IR spectroscopy, X-ray crystallography, and elemental analysis.

Tetranuclear hydroxo-bridged copper(II) cluster of the Z type: Preparation and structural and magnetic characterization of [(Cu 4 bipy 4 (OH) 4 (B 10 H 10 ) 2 (DMSO) 2 ]

(n = 6, 10, 12) has been isolated and character ized, namely, [(аguH)2]0.388[Cu(аgu)2]6.12(B12H12)] (agu is aminoguanidine, I) [5, 8]. According to X ray dif fraction data [8], compound I has a nontrivial struc ture consisting of polymeric chains composed of alter nating [Cu(agu)2B12H12] and (aguH)2B12H12 units. In the present paper, we propose a general proce dure for synthesizing Cu(II) complexes with the

anti-syn and anti-anti coordination of the bridging CO32− group in [Cu2(Phen)4(μ-CO3)]B10H10 binuclear complexes: Synthesis, structure, and magnetic properties

A redox reaction that occurs in the [Cu2B10H10]/Phen system in CH3CN/DMSO and CH3CN/DMF in air yields a Cu(II) binuclear complex, [(Phen)2Cu(CO3)Cu(Phen)2]2+. The [Cu2(Phen)4(μ-CO3)]B10H10 · 2.5DMSO · 2H2O (I) and [Cu2(Phen)4(μ-CO3)]B10H10 · 4DMF (II) compounds have been isolated and studied by X-ray crystallography at 150 K and EPR at 295 K. Their magnetic properties have been studied in the range 300–2 K. In the cations of both compounds, the bridging CO32− group is bidentately coordinated to two Cu atoms. The cations in I and II have different spatial orientations of the Cu-O bonds: anti-syn and anti-anti, respectively. Compound I has weak magnetic interactions caused by a short Cu…Cu distance (4.441 Å) in the dimer. No exchange coupling is observed in II.

Reversible single-crystal-to-single-crystal photoisomerization of a silver(I) macropolyhedral borane

We report a new family of photoactive molecular compounds for which reversible solid state transformations and linkage isomerism have been observed using in situ X-ray diffraction. The interaction of tris(triphenylphosphine)silver(I) with eicosaborate [B20H18]2− afforded a binuclear complex with a bridging boron cluster that underwent a series of isomerization transformations occurring in a single-crystal-to-single-crystal manner without crystal degradation and obeying the criteria for an effective molecular switch.

Interactions of sodium liquid glass with triethylammonium decahydro-closo-decaborate (Et3NH)2B10H10

Reactions of sodium silicates of liquid glass (LG) with closo-triethylammonium decaborate (Et3NH)2B10H10 were studied over a wide range of component ratios LG/(Et3NH)2B10H10 of 95/5, 85/15, 70/30, 60/40, 50/50, 40/60, and 26/74 wt/wt. IR spectroscopy showed that the introduction of anion into the LG gives rise to the formation of a three-dimensionally branched system of multicenter bonds:

Behavior of dodecahydro-closo-dodecaborate anion B12H122− in reaction with Au(Ph3P)Cl

B - H^{\delta - } \cdots H^{\delta + } - O - H^{\delta + } \cdots O^{\delta - } - Si

Nickel(II) complexes with boron cluster anions [B n H n ]2– (n = 10, 12) and azaheterocyclic ligands L (L = Bipy, Phen, BPA, and DAB)

and

Cobalt(II) and nickel(II) complexes with 1-methyl-2-pyridin-2-yl-1H- and 1-methyl-2-phenyliminomethyl-1H-benzimidazoles and the closo-decaborate anion

B - H^{\delta - } \cdots H^{\delta + } - O \cdots H - O - H \cdots O^{\delta - } - Si