Section 54
Chapter 53,526

Heteroatomic deltahedral clusters: synthesis and structures of closo-[Bi3Ni (4) (CO) 6]3-, closo-[Bi4Ni4 (CO) 6]2-, the open cluster [Bi3Ni6 (CO) 9]3-, and the intermetalloid closo-[[email protected][Bi6Ni6 (CO) 8) ]4-

Goicoechea, J.M.; Hull, M.W.; Sevov, S.C.

Journal of the American Chemical Society 129(25): 7885-7893


ISSN/ISBN: 0002-7863
PMID: 17550250
DOI: 10.1021/ja071044b
Accession: 053525284

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Reactions of ethylenediamine solutions of K4Bi5 with Ni(PPh3)2(CO)2 yielded four novel hetero-atomic Bi/Ni deltahedral clusters. Three of them, the 7-atom pentagonal bipyramidal [Bi3Ni4(CO)6]3-, the 8-atom dodecahedral [Bi4Ni4(CO)6]2-, and the Ni-centered or empty 12-atom icosahedral [[email protected][Bi6Ni6(CO)8]4-, are closo-species according to both electron count and shape. The centered icosahedral cluster resembles packing in intermetallic compounds and belongs to the emerging class of intermetalloid clusters. The shape of the fourth cluster, [Bi3Ni6(CO)9]3-, can be derived from the icosahedral Ni-centered [[email protected][Bi6Ni6(CO)8]4- by removal of three Bi- and one Ni-atoms of two neighboring triangular faces. The clusters were structurally characterized by single-crystal X-ray diffraction in compounds with potassium cations sequestered by 2,2,2-crypt or 18-crown-6 ether. They were also characterized in solution by electrospray mass spectrometry.

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