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Issue 35, 2006
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NiN2S2 complexes as metallodithiolate ligands to RhI, RhII and RhIII§

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Abstract

Three molecular structures are reported which utilize the NiN2S2 ligands Ni-1, (bis(mercaptoethyl)diazacyclooctane)nickel and Ni-1′, bis(mercaptoethyl)diazacycloheptane)nickel, as metallodithiolate ligands to rhodium in oxidation states I, II and III. For the RhI complex, the NiN2S2 unit behaves as a bidentate ligand to a square planar RhI(CO)(PPh3)+ moiety with a hinge or dihedral angle (defined as the intersection of NiN2S2 and S2Rh(C)(P) planes) of 115°. Supported by Ni-1ligands, the RhII oxidation state occurs in a dirhodium C4 paddlewheel complex wherein four NiN2S2 units serve as bidentate bridging ligands to two singly-bonded RhII ions at 2.893(8) Å apart. A compilation of the remarkable range of M–M distances in paddlewheel complexes which use NiN2S2 complexes as paddles is presented. The RhIII state is found as a tetrametallic [Rh(Ni-1′)3]3+ cluster, roughly shaped like a boat propeller and structurally similar to tris(bipyridine)metal complexes.

Graphical abstract: NiN2S2 complexes as metallodithiolate ligands to RhI, RhII and RhIII

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Supplementary files

Article information


Submitted
24 Apr 2006
Accepted
27 Jun 2006
First published
19 Jul 2006

Dalton Trans., 2006, 4244-4252
Article type
Paper

NiN2S2 complexes as metallodithiolate ligands to RhI, RhII and RhIII

S. P. Jeffery, K. N. Green, M. V. Rampersad, J. H. Reibenspies and M. Y. Darensbourg, Dalton Trans., 2006, 4244 DOI: 10.1039/B605768C

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