The compound (NMe4)3[Rh14H(CO)25] · Me2CO has been obtained by treatment of (NMe4)4[Rh14(CO)25] with acids. The (NMe4)+ salt of the trianion, containing solvated acetone molecules, crystallizes in the orthorhombic Pmcn space group (non-standard setting of Pnma, No. 62), with a 16.436(2), b 17.655(4), c 21.490(4) Å and Z = 4. The structure was refined by full-matrix least-squares, on the basis of 3472 significant unique reflections, to a final R value of 0.056. The anion shows a structure related to that of the parent [Rh14(CO)25]4-, which is a distorted fragment of body-centered cubic packing with C4υ symmetry. However, the insertion of the hydride ligand in an interstitial position, confirmed also by NMR studies, causes significant changes both in the metallic skeleton and in the CO stereochemistry, reducing the overall symmetry to Cs. The RhRh distances are scattered. The central metal exhibits 8 short (mean 2.657 Å), two normal (2.878(1) Å and three very long (mean 3.258 Å) contacts with the surface metals. The RhRh surface interactions range from 2.692(1) to 3.356(2) Å. The metal atom polyhedron can be described as intermediate between a body-centered cubic and a closest-packed entity. The carbonyl ligands are bound 10 terminally (mean RhC and CO 1.86 and 1.15 Å), 13 almost symmetric double-bridging (mean RhC and CO 2.01 and 1.17 Å), and two markedly asymmetric double-bridging (short RhC 1.89(2), long RhC 2.41(2) and CO 1.16(2) Å). The structure is compared with those of related high-nuclearity rhodium clusters. © 1989.
|Titolo:||High nuclearity carbonyl clusters of rhodium. Synthesis and crystal structure of (NMe4)3[Rh14H(CO)25] · Me2CO|
CIANI, GIANFRANCO MARIA (Primo)
SIRONI, ANGELO AGOSTINO DANIELE (Penultimo)
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||1989|
|Digital Object Identifier (DOI):||10.1016/0022-328X(89)88052-0|
|Appare nelle tipologie:||01 - Articolo su periodico|