Alkyne-vinylidene coupling in the reactions of the alkyne complex Os3(μ-CO)(CO)9(μ3-Me3C2Me) with Me3SiC≡CR (R=Me, Bun). The structure and stereodynamic behavior of clusters Os3(CO)9{μ3-C(SiMe3)=C(Me)C=C(SiMe3)=C(Me)C=C(SiMe3)R} containing an osmacyclobutene moietycontaining an osmacyclobutene moiety

Reactions of the alkyne cluster Os₃(μ-CO)(CO)₉(μ₃-Me₃C₂Me) with alkynes Me₃SiC≡CR (R=Me, Buⁿ) in refluxing hexane result in the formation of clusters Os₃(CO)₉{μ₃-C(SiMe₃)=C(Me)C=C(SiMe₃)=C(Me)C=C(SiMe₃)R} (2a: R=Me;3a: R=Buⁿ). The dienediyl ligand in these complexes is formed by alkyne-vinylidene coupling, with vinylidene generated in the course of reaction from the alkyne molecule by the acetylene-vinylidene rearrangement involving a 1,2-shift of the Me₃Si group. The structure of cluster3a was determined by X-ray structural analysis. The dienediyl ligand is coordinated to three metal atoms of the cluster framework by two π-ethylene bonds with two osmium atoms and two σ-bonds with the third osmium atom with the formation of the osmacyclobutene moiety. The¹H and¹³C NMR study of¹³CO-enriched samples of clusters2a and3a revealed the stereochemical nonrigidity of these molecules due to the exchange of the hydrocarbon and carbonyl ligands.     

Unexpected formation of clusters with a nortricyclene-containing carborane ligand, 1-(η6-arene)-3-(C7H9CH2O)-isonido-1,2,4-RuC2B8H9, in the reaction of 1,1,3-(PPh3)3-1-H-1,2,4-RuC2B8H9 with 2-(hydroxymethyl)norbornadiene in arene solvents

Heating of 1,1,3-(PPh₃)₃-1-H-1,2,4-RuC₂B₈H₉ with 2-(hydroxymethyl)bicyclo[2.2.1]hepta-2,5-diene in arene solvents (benzene, toluene, or mesitylene) unexpectedly afforded the ruthenium arene complexes 1-(η⁶-arene)-3-(C₇H₉CH₂O)-isonido-1,2,4-RuC₂B₈H₉ containing the nortricyclene fragment in the carborane ligand.     

Coordination chemistry of anticrowns: Complexation of cyclic trimeric perfluoro-o-phenylenemercury with nitro compounds

Cyclic trimeric perfluoro-o-phenylenemercury (o-C₆F₄Hg)₃ (1) is capable of reacting with nitromethane to give complex {[(o-C₆F₄Hg)₃](CH₃NO₂)} (2) containing one molecule of the nitro compound per one macrocycle molecule. In this complex, the nitromethane ligand is bound to 1 by its both oxygen atoms, one of which is simultaneously coordinated to all three Hg centres of the macrocycle while the other interacts with a single Hg centre. The complex of similar composition, {[(o-C₆F₄Hg)₃](C₆H₅NO₂)} (3), is produced in the interaction of 1 with nitrobenzene. In this complex too, the both oxygen atoms of the nitro group are involved in the bonding to the macrocycle. A distinctive feature of 3 is that here one oxygen atom of the coordinated nitro derivative is bound by only two Hg centres of 1 whereas the other interacts again with a single Hg site. The reaction of 1 with 5-nitroacenaphthene affords a 1:1 complex, {[(o-C₆F₄Hg)₃](C₁₂H₉NO₂)} (4), having a polydecker sandwich structure in the crystal. Unlike in 3, the aromatic rings of the nitroarene units in 4 are disposed virtually in parallel to the macrocycles. The nitro compound in 4 behaves again as a bidentate ligand, forming three Hg-O bonds with one of the adjacent macrocycles and a single Hg-O bond with another molecule of 1. The complex is characterized also by shortened Hg-C contacts between the Hg centres of 1 and the carbon atoms of the nitroarene moiety as well as shortened C-C contacts between the carbon atoms of the nitroarene and the macrocycle. In the interaction of 1 with 1-nitropyrene, complexes of two compositions, viz. {[(o-C₆F₄Hg)₃](C₁₆H₉NO₂)} (5) and {[(o-C₆F₄Hg)₃](C₁₆H₉NO₂)₃} (6) are formed. An X-ray diffraction study of 6 has shown that in this adduct two of three coordinated molecules of the nitro compound are located on one side of the metallacycle plane while the third nitroarene molecule is disposed on its other side. The aromatic rings of all three nitropyrene ligands in 6 are practically parallel to the mean plane of the macrocycle. In contrast to 2-4, each molecule of the nitroarene in 6 is bonded to 1 by a single oxygen atom which is coordinated only to one Hg centre. In the case of one of the nitropyrene ligands that forms much longer Hg-O bond with 1 than two others, an additional contribution to the bonding is made by shortened Hg-C contacts between the macrocycle and the carbon atoms of the aromatic pyrene core and also by shortened C-C contacts between the carbon atoms of the coordinated nitroarene and 1. The synthesized adducts are the first examples of complexes of an anticrown with nitro compounds.     

Stable exo-nido-metallacarboranes (M = Os(IV)) that incorporate meta-carborane-based dicarbollide ligands

Reactions of the [K]+ salts of the [nido-7,9-C2B9H12]- anion (2) and its C-phenylated derivative [7-Ph-nido-7,9-C2B9H11]- (4) with [OsCl2(PPh3)3] (3) proceed in benzene at ambient temperature with the formation of 16-electron chlorohydrido-Os(IV) exo-nido complexes, [exo-nido-10,11-{(Ph3P)2OsHCl}-10,11-(mu-H)2-7-R-7,9-C2B9H8] (5: R = H; 6: R = Ph), along with the small amounts of the charge-compensated nido-carboranes [nido-7,9-C2B9H11PPh3] (7) and [7-Ph-nido-7,9-C2B9H10PPh3] (8) as byproducts. However, when carried out under mild heating in ethanol, the reaction of 2 with 3 selectively afforded a 16-electron dihydrido-Os(IV) exo-nido complex [exo-nido-10,11-{(Ph3P)2OsH2}-10,11-(mu-H)2-7,9-C2B9H9] (9). Structures of both complexes 5 and 9 have been confirmed by single-crystal X-ray diffraction studies, which revealed that nido-carboranes in these species function as a bidentate dicarbollide ligands [7-R-nido-7,9-C2B9H10]2- linked to the Os(IV) center via two B-H...Os bonds involving adjacent B-H vertices in the upper CBCBB belt of the carborane cage. Thus, compounds 5 and 9 represent the first structurally characterized exo-nido-metallacarboranes based on meta-dicarbollide-type ligands. Variable-temperature 1H and 31P{1H} NMR experiments indicate that complex 9 is fluxional in solution and shows an unusual exchange between terminal Os-(H)2 and bridging {B-H}2...Os hydrogen atoms. Upon heating in d8-THF at 65 degrees C, complex 9 converts irreversibly to its closo isomer [2,2-(PPh3)2-2,2-H2-closo-2,1,7-OsC2B9H11] (13), which could thus be obtained as a pure crystalline solid. The structure of 13 has been established on the basis of analytical and multinuclear NMR data and a single-crystal X-ray diffraction study.     

The first example of cobalt(III) μ-oxoacetate with water molecules in apical positions

Oxidation of Co(MeCOO)₂·4H₂O with ozone in acetic acid followed by the treatment with nitric acid results in the formation of the trinuclear oxo-centered acetate complex [Co^III ₃(μ₃-O)(μ-O₂CMe)₆(OH₂)₃] NO₃·MeCOOH ([I]NO₃·MeCOOH). Reasons of a decrease in the idealized symmetry of molecular structure (D _3h → D ₃) of the complex cation [I]⁺ were analyzed by means of quantum-chemical calculations. The complex does not retain its structure in solutions (in water, methanol, and ethanol).     

Structural Studies of Novel Coordination Compounds Run in the Nesmeyanov Institute of Organoelement Compounds,Russian Academy of Sciences

In this paper, selected results of the structural and theoretical studies of different types of coordination compounds synthesized in the Laboratory of X-ray Structural Studies of the Nesmeyanov Institute of Organoelement Compounds (NIOC), Russian Academy of Sciences (Center for X-ray Structural Studies in the General and Technical Chemistry Division, RAS) are presented.     

Diastereoselective Synthesis of Highly Functionalized Proline Derivatives

An efficient way to access highly functionalized proline derivatives was developed based on a Cu(I)-catalyzed reaction between CF₃-substituted allenynes and tosylazide, which involved a cascade of [3 + 2]-cycloaddition/ketenimine and a rearrangement/Alder-ene cyclization to afford the new proline framework with a high diastereoselectivity.     

New all-cis-tetra(p-tolyl)cyclotetrasiloxanetetraol and its functionalization

New all-cis-tetra(p-tolyl)cyclotetrasiloxanetetraol and its derivatives with Si(CH = CH₂)Me and Si(H)Me₂ groups have been prepared and characterized by IR and NMR spectroscopy, GPC, mass spectrometry, TGA and DSC. Molecular and crystalline structures of the tetraol and its derivative with four Si(CH = CH₂)Me groups have been determined by single-crystal X-ray diffraction.     

Orientation in the metalation of amide, carbamate, ureido, and allylic derivatives of cymantrene

The orientation in the metalation of monosubstituted carbamate-, amide-, ureido-, and allyl-containing derivatives of cymantrene was determined for the first time. The data obtained open up a synthetic route to polyfunctional 1,2- and 1,3-disubstituted cymantrenes. They can serve as the starting materials for the preparation of chelate complexes of (dicarbonyl)-(cyclopentadienyl)manganese, which hold promise as novel organometallic photochromes. A method for the synthesis of earlier unknown chiral derivatives of cymantrene with a quaternary carbon atom in position 1 of the side chain was proposed.