617-77-6Relevant articles and documents
New noncentered icosahedral nickel-bismuth carbonyl clusters: Geometric analysis of the homologous [Ni10(EMe)2(CO)18]2- dianions (E = P, As, Sb, Bi) containing noncentered 1,12-Ni10E2 icosahedral cages
Mlynek, Peter D.,Dahl, Lawrence F.
, p. 1655 - 1667 (1997)
The designed reaction of [Ni6(CO)12]2- (1) with MeBiCl2 in THF at low temperature (-78 °C) has given rise to the desired [Ni10(BiMe)2(CO)18]2- dianion (2) as the major product (ca. 45% yield). This sought-after (methylbismuthinidene)nickel carbonyl cluster containing a noncentered 1,12-Ni10Bi2 icosahedral cage is the missing member of the known homologous [Ni10(EMe)2(CO)18]2- series (E = P, As, Sb) whose members differ from one another only by the substitution of two bridging E atoms of the congeneric main-group V (15) elements into the two centrosymmetrically related (opposite) vertices of the icosahedral cage. The formulation of 2 in the [NMe4]+ salt was established unambiguously from X-ray crystallography and ascertained from a complete elemental analysis. This air-sensitive brown compound was also characterized by IR, cyclic voltammetry, negative-ion ESI mass spectrometry, and low-temperature 13C{1H} and 1H NMR spectroscopy. The [NMe4]+ salt of the ethylbismuthinidene [Ni10(BiEt)2(CO)18]2- (3) was similarly prepared, isolated, and structurally determined via a single-crystal X-ray diffraction study. Solid-state magnetic susceptibility measurements conclusively showed 2 (in the [NMe4]+ salt) to be diamagnetic at room temperature in accordance with it (and the other homologous members) being electronically equivalent (isolobal) with the classic regular icosahedral [B12H12]2- dianion in likewise possessing 13 skeletal electron pairs. A detailed comparison of the essentially identical molecular parameters of 2 and 3 with those of the three other isostructural [Ni10(EMe)2(CO)18]2- clusters (E = P, As, Sb) provides illuminating information regarding particular geometric changes in the empty icosahedral 1,12-Ni10E2 cages arising from a systematic size variation in the two E atoms of the four congeneric group V (15) elements. Moreover, a comparative analysis of the molecular parameters of 2 with those of the previously reported [Ni11Bi2(CO)18]3- trianion (4), which contains a Ni-centered (filled) 1,-12-Ni10Bi2 icosahedral cage, reveals marked geometric distortions upon the formal insertion of a centered (interior) Ni(i) into the icosahedral cage. Variable-temperature 13C{1H} NMR spectra of 2 in acetone-d6 show fast terminal-bridge carbonyl exchange of the 18 COs at room temperature but limiting slow exchange at low temperature (-60 °C), as was also found for [Ni10(EMe)2(CO)18]2- (E = P, Sb) previously.
Hoffmann, P.,Baechmann, K.,Lieser, K. H.,Klenk, H.
, p. 577 - 582 (1971)
Frankland, E.,Duppe, B. F.
, p. 29 - 36 (1864)
Syntheses and solid-state structures of Et2SbTeEt and Et2BiTeEt
Heimann, Stefan,Kuczkowski, Andreas,Bl?ser, Dieter,W?lper, Christoph,Haack, Rebekka,Jansen, Georg,Schulz, Stephan
supporting information, p. 4858 - 4864 (2015/03/31)
Diethylstibanyl- and diethylbismuthanyl telluranes Et2MTeEt (M = Sb 1, Bi 2) as well as tBu3Sb (3) were structurally characterized by single-crystal X-ray diffraction. Single crystals of 1-3 were grown by using an IR-laser-assisted t
