ALKYNE COMPLEXES OF PLATINUM. PART 5. DI- AND TRI-PLATINUM COMPLEXES WITH BRIDGING TRIMETHYLSILYL-SUBSTITUTED ALKYNE LIGANDS; CRYSTAL STRUCTURE OF

DOI: 10.1039/DT9810000862

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 862 - 872 (1981)

Update date:2022-07-30

Topics:

Authors:

Boag, Neil M.

Green, Michael

Howard, Judith, A. K.

Stone, F. Gordon A.

Wadepohl, Hubert

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Article abstract of DOI:10.1039/DT9810000862

Bis(trimethylsilyl)acetylene in excess reacts with (cod = cyclo-octa-1,5-diene) to give the diplatinum complex , whereas and the alkyne afford .Reactions of with the alkynes RCCSiMe3 (R = SiMe3, SiMe2Bu^t, CF3 or Ph) in 2:1 mol ratio, or excess of alkyne in the case of CF3CCSiMe3, yields the diplatinum complexes .The nickel compounds (R = SiMe3 or Ph) have also been prepared.Reaction of PhCCSiMe3 with in 1:1 mol ratio gives the triplatinum complex ,which like undergoes dynamic behaviour in solution, as revealed by variable-temperature n.m.r. studies.An X-ray crystallographic study on the latter was carried out.Crystals are monoclinic, space group P2₁/c, Z = 4, in a unit cell of dimensions a = 14.93(1), b = 10.38(1), c = 17.463(8) Angstroem, β = 112.79(6)deg.The structure has been refined to R 0.038 (R' 0.038) for 5 464 unique reflections to 20 <= 60 deg (Mo-K_α,X-radiation) collected at 200 K.The PhC2SiMe3 ligand transversely bridges the Pt...Pt vector (2.914 Angstroem) such that the dihedral angle between the two planes formed by the two Pt-μ-C2 units is 97 deg.This, together with the long metal-metal distance and the essentially planar geometry about each platinum atom, is taken to imply little or no direct Pt-Pt bonding, with the two halves of the molecule held together by orthogonal ? orbitals of the shared PhCCSiMe3 ligand.

Full text of DOI:10.1039/DT9810000862

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