Icosahedral carbonyl clusters [Ni10Sb2(µ12-Ni){Ni(CO)3}2-(CO)18]n–(n= 2, 3 or 4); synthesis, spectroscopic, electrochemical and bonding analysis. Crystal structures of [Ni10Sb2(µ12-Ni){Ni(CO)3}2(CO)18]n–(n= 2 or 3)
- 1 January 1991
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. S,p. 739-748
- https://doi.org/10.1039/dt9910000739
Abstract
The new [Ni13Sb2(CO)24]n–(n= 2, 3 or 4) cluster anions have been isolated from the reaction of [Ni6(CO)12]2– with SbCl3 and have been characterized spectroscopically and electrochemically. Their structures (n= 2 or 3), elucidated by X-ray diffraction studies, consist in Ni-centred icosahedral [Ni11Sb2(CO)18]n– moieties which display an unexpected electron count and formally behave as ‘exotic’ distibine bridging ligands. The compound [N(PPh3)2]2[Ni13Sb2(CO)24] is triclinic, space group P, with a 13.134(3), b 13.546(2), c 15.416(2)Å, α= 109.54(1), β= 91.47(2), γ= 101.68(1)° and Z= 1; final R 0.030. Compound [NMe3(CH2Ph)]4[Ni13Sb2(CO)24]Cl is monoclinic, space group C2/c, with a 20.615(4), b 15.508(3), c 25.805(19)Å, β= 99.21(4)° and Z= 4; final R 0.034. A bonding analysis of icosahedral nickel carbonyl clusters centred by a transition or a main group element, as well as non-centred, has been carried out. This indicates the relevance of both the cavity occupation and the number of ligands and the associated stereogeometry in determining the number of cluster valence electrons.Keywords
This publication has 35 references indexed in Scilit:
- Reactions of the [Ni6(CO)12]2- dianion with stibine and bismuthine reagents: synthesis and stereophysical characterization of the [Ni10(SbPh)2(CO)18]2- dianion containing a noncentered icosahedral Ni10Sb2 core and Ni2(CO)4(μ2-Ph2SbOSbPh2)2 containing a centrosymmetric eight-membered (NiSbOSb)2 ringJournal of Organometallic Chemistry, 1990
- Nickel carbonyl clusters containing interstitial carbon-congener atoms: synthesis and structural characterisation of the [Ni12(µ12-E)(CO)22]2–(E = Ge, Sn) and [Ni10(µ10-Ge)(CO)20]2–dianionsJournal of the Chemical Society, Chemical Communications, 1989
- Cluster of Clusters: Structure of the 37‐Atom Cluster [(p‐Tol3P)12Au18Ag19Br11]2⊕ and a Novel Series of Supraclusters Based on Vertex‐Sharing IcosahedraAngewandte Chemie International Edition in English, 1987
- Synthesis and structural characterization of the [Ni9(AsPh)3(CO)15]2- and [Ni10(AsMe)2(CO)18]2- dianions containing noncentered icosahedral Ni12-xAsx cores (x = 2, 3): electronically equivalent metal cluster analogs of the regular icosahedral [B12H12]2- dianionJournal of the American Chemical Society, 1986
- Novel triicosahedral structure of the largest metal alloy cluster: hexachlorododecakis(triphenylphosphine)-gold-silver cluster [(Ph3P)12Au13Ag12Cl6]m+Journal of the American Chemical Society, 1984
- Synthesis and structural characterization of [Au9{P(p-C6H4OMe)3}8](BF4)3; a cluster with a centred crown of gold atomsJournal of the Chemical Society, Chemical Communications, 1982
- [Rh12Sb(CO)27]3-. an example of encapsulation of antimony by a transition metal carbonyl clusterJournal of Organometallic Chemistry, 1981
- Synthesis and X-ray structural characterization of the centred icosahedral gold cluster compound [Aul3(PMe2Ph)10Cl2](PF6)3; the realization of a theoretical predictionJournal of the Chemical Society, Chemical Communications, 1981
- High nuclearity carbonyl clusters of rhodium. Part 2. Crystal and molecular structure of the tetramethylammonium salt of dodeca-µ-carbonyl-dodecacarbonylhydrido-polyhedro-tridecarhodate(4–)–1-methylpyrrolidin-2-one (1/3)J. Chem. Soc., Dalton Trans., 1981
- Molecular-orbital calculations on cluster compounds of goldJ. Chem. Soc., Dalton Trans., 1976