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Synthesis of Mixed-metal Clusters by the Reaction of the Unsaturated Cluster with Transition-metal Hydrides: the X-Ray Crystal Structures of > and >

DOI: 10.1039/DT9840002111

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2111 - 2118 (1984)

Update date:2022-08-04

Topics:

Authors:

Johnson, Brian F. G.Johnson, Brian F. G.

Lewis, JackLewis, Jack

Raithby, Paul R.Raithby, Paul R.

Azman, S. N.Azman, S. N.

Syed-Mustaffa, B.Syed-Mustaffa, B.

et al.et al.

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Article abstract of DOI:10.1039/DT9840002111

The co-ordinatively unsaturated dihydride cluster reacts with the transition-metal hydrides <6>, , , and 2> to give the mixed-metal clusters > (1), > (2), > (3), and >> (4).These complexes have been characterized by i.r. and n.m.r. spectroscopy, and the structures of (1) and (2) have been established by single-crystal X-ray analysis.In complex (1) the three Os atom lie at the vertices of an isosceles triangle the long edge <3.026(3) Angstroem> of which is bridged by the Cu atom of the Cu(PPh3) ligand.The hydrides were not located directly but evidence suggests that they bridge the long Os - Os bond and the two Os - Cu bonds.The carbonyl arrangement is similar to that observed in .In complex (2) the Ir atom caps the Os3 triangle to form a distorted tetrahedral metal framework.The three Ir - Os bond lengths <2.759(3), 2.789(2), and 2.917(3) Angstroem> show considerable variation.The distribution of the eleven terminal carbonyl ligands and the phosphine group, which is co-ordinated to the Ir atom, indicates that the three hydrides bridge the two longer Os - Os bonds, and the longest Os - Ir bond.From the spectroscopic data the overall geometry of complex (3) is closely related to that of (2), while (4) has a tetrahedral metal arrangement with hydrides and carbonyl groups bridging Os - Os and Os - Ni edges.

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