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An approach to megalo-boranes. Mixed and multiple cluster fusions involving iridaborane and platinaborane cluster compounds. Crystal structure determinations by conventional and synchrotron methods

Lookup NU author(s): Emeritus Professor Bill CleggORCiD


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Several new macropolyhedral metallaboranes have been isolated from thermolytic mixed cluster fusion reactions involving metallaboranes and molten B10H14 as solvent. Co-thermolysis of B10H14 with nine-vertex [(CO)(PMe3)2HIrB8H12] (1) engenders 18-vertex [(CO)(PMe3)2IrB17H20] (3), via double cluster fusion; this has the 18-vertex configuration of syn-B18H22, but with a metal atom in the 10-position. From the same reaction, triple cluster fusion engenders 28-vertex [(PMe3)2IrB26H24Ir(CO)(PMe 3)2] (4), which structurally is based on an intimate interfusion of closed 10-vertex and 12-vertex subclusters, to generate a tetrahedral tetraboron core that also has a more open commo one-boron linkage to a nido nine-vertex {IrB8} subcluster. Compound 4 exhibits interesting consequences of cluster-crevice formation and introduces the concept of globular megalo-borane structures that have borons-only cores surrounded by boron-hydride sheaths. Examination for incipient megalo-borane globular behaviour in another system, viz. [IrCl(PPh3)3] (7) with anti-B18H22, reveals a four-atom core feature in 19-vertex [(PPh3)HIrB18H18(PPh3)] (6), which has a closo-type {IrB10} 11-vertex subcluster fused to a nido 10-vertex {B10} subcluster to generate a four-atom {IrB3} tetrahedron. Examination for mixed cluster fusion in other systems reveals the generation of [(PMe2Ph)2Pt-anti-B18H20] (8), from the co-thermolysis of [(PMe2Ph)2PtB8H12] (2) and B10H14, and examination for multiple cluster fusion reveals the formation of 30-vertex [(PMe2Ph)2(PMe2C6H4) 2Pt2B28H32] (10), 29-vertex [(PMe2Ph)2PtB28H32] (11) and 27-vertex [(PMe2Ph)2PtB26H26(PMe 2Ph)] (12) from the same reaction. Structurally, compound 10 is based on a 10-vertex arachno-{6,9-Pt2B8} unit linked, via one B-B two-electron two-centre bond each, to two 10-vertex nido-{B10} units; it also exhibits molecular condensation in the form of two P-phenylene ortho-cycloboronations. Compound 11 is based on the 19-vertex [(PMe2Ph)2Pt-η4-anti-B18H 22] configuration with an additional 10-vertex nido-{B10H13} moiety bound to the non-platinated subcluster via one B-B two-electron two-centre bond. Compound 12 is based on two nido 11-vertex {PtB10} units joined by a single commo Pt vertex, with one of these units conjoined to an arachno eight-boron unit via a two-boron common edge and an open bridging {B-H(exo)-Pt-μ-B2} link. Thermolysis of [(PMe2Ph)2PtB8H12] (2) with the pre-formed double-cluster compound anti-B18H22 generates triple-contiguity 27-vertex [(PMe2Ph)PtB26H26(PMe2Ph)] (13) which, structurally, consists of a nido 11-vertex {PtB10} unit that is fused to a second 11-vertex nido {PtB10} unit with a triangular {PtB2} face in common, and also fused to a 10-vertex nido {B10} unit with a {B2} edge in common. The sequence 12→11→10→13→4 represents a progression of increasing intimacy of cluster fusion. Small crystals of compounds 3, 11 and 12 necessitated synchrotron X-radiation for sufficient diffraction intensity. © 1999 Elsevier Science S.A.

Publication metadata

Author(s): Bould J, Clegg W, Teat SJ, Barton L, Rath NP, Thornton-Pett M, Kennedy JD

Publication type: Article

Publication status: Published

Journal: Inorganica Chimica Acta

Year: 1999

Volume: 289

Issue: 1-2

Pages: 95-124

Print publication date: 15/06/1999

ISSN (print): 0020-1693

ISSN (electronic): 1873-3255

Publisher: Elsevier BV


DOI: 10.1016/S0020-1693(99)00071-7


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