Multiple nitrene insertions into metal–sulfur bonds of dithiocarbamate complexes: synthesis of sulfido-amido and zwitterionic tetraamido complexes

Graeme Hogarth; K. Travis Holman; Andrew Pateman; Andrea Sella; Jonathan W. Steed; Idris Richards

doi:10.1039/B503004H

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Dalton Transactions

Issue 16, 2005

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Multiple nitrene insertions into metal–sulfur bonds of dithiocarbamate complexes: synthesis of sulfido-amido and zwitterionic tetraamido complexes

Graeme Hogarth , K. Travis Holman , Andrew Pateman , Andrea Sella , Jonathan W. Steed and Idris Richards

Dalton Trans., 2005, 2688-2695

DOI: 10.1039/B503004H
Received 28 Feb 2005, Accepted 23 Jun 2005
First published on the web 07 Jul 2005

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The iodine(III) reagent, PhI [double bond, length as m-dash] NTs, acts as a source of the nitrene fragment NTs, which undergoes facile insertion into the metal–sulfur bonds of a range of dithiocarbamate complexes. Addition of two equivalents of PhINTs to [M(S₂CNR₂)₂] affords sulfido-amido complexes [M{SC(NR₂)SNTs}₂] (M [double bond, length as m-dash] Ni, Cu), which insert two further nitrene fragments to afford zwitterionic tetraamido complexes [M{TsNSC(NR₂)SNTs}₂] (MCo, Ni, Cu). Crystallographic studies have been carried out on both types of complex allowing possible resonance hydrids of the new ligand types to be assessed.

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Graeme Hogarth
K. Travis Holman
Andrew Pateman
Andrea Sella
Jonathan W. Steed
Idris Richards

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Dalton Transactions

Multiple nitrene insertions into metal–sulfur bonds of dithiocarbamate complexes: synthesis of sulfido-amido and zwitterionic tetraamido complexes

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