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Issue 10, 2011

Organometallic dithiolene complexes of the group 8–10 metals: Reactivities, structures and electrochemical behavior

Author affiliations

Abstract

Research progress in the organometallic dithiolene complexes such as [Cp(or Cp*)M(dithiolene)] (M = Co, Rh, Ir, Ni), [(C6R6)Ru(dithiolene)] and [(C4R4)Pt(dithiolene)] complexes during the past decade is described and the reactivities, structures and electrochemical behavior are summarized in this paper. The five-membered metalladithiolene ring (MS2C2) undergoes addition reactions to the M[double bond, length as m-dash]S bond to form 18-electron adducts by an imido, alkylidene, alkene or norbornene group and also undergoes dimerizations on the basis of the unsaturation in the ring. The aromaticity of the ring causes substitution reactions on the dithiolene carbon by a C-centered radical, S-centered radical or succinimide group when the ring has a C–H bond. Furthermore a dithiolenedithiolene homo-coupling reaction by an acid or dithiolene–aryl cross-coupling occurs based on the aromaticity in the ring. Dissociations of the 18-electron adducts are observed by those thermolyses, photolyses, electrochemical redox reactions and other chemical reactions with tertiary phosphorus compounds. One representative example of them is the imido adduct dissociation with PR3 under heating toward the intramolecular imido migration to a Cp ligand. Since all products are rearomatized by those adduct dissociations, it is concluded that the ‘coexistence of aromaticity and unsaturation’ in the metallacycle mediates the diverse chemical reactions.

Graphical abstract: Organometallic dithiolene complexes of the group 8–10 metals: Reactivities, structures and electrochemical behavior

Supplementary files

Article information


Submitted
16 Aug 2010
Accepted
25 Jan 2011
First published
10 Feb 2011

Dalton Trans., 2011,40, 2112-2140
Article type
Perspective

Organometallic dithiolene complexes of the group 8–10 metals: Reactivities, structures and electrochemical behavior

M. Nomura, Dalton Trans., 2011, 40, 2112 DOI: 10.1039/C0DT01025A

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