Multiple nitrene insertions into metal-sulfur bonds of dithiocarbamate complexes: synthesis of sulfido-amido and zwitterionic tetraamido complexes.
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 PhI=NTs to [M(S(2)CNR2)2] affords sulfido-amido complexes [M{SC(NR2)SNTs}2](M=Ni, Cu), which insert two further nitrene fragments to afford zwitterionic tetraamido complexes [M{TsNSC(NR2)SNTs}2](M=Co, 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.
Hogarth
Graeme
G
Department of Chemistry, University College London, 20 Gordon Street, London, UK WC1H 0AJ. g.hogarth@ucl.ac.uk
Holman
K Travis
KT
Pateman
Andrew
A
Sella
Andrea
A
Steed
Jonathan W
JW
Richards
Idris
I
D000577:Amides / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry; D003300:Copper / Q000737:chemistry; D018360:Crystallography, X-Ray; D007097:Imines / Q000737:chemistry*; D019216:Metals, Heavy / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009532:Nickel / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013455:Sulfur / Q000737:chemistry*; D013859:Thiocarbamates / Q000737:chemistry*
D000577:Amides; D007097:Imines; D019216:Metals, Heavy; D009942:Organometallic Compounds; D013859:Thiocarbamates; C017621:phenylnitrene; D003035:Cobalt; D013455:Sulfur; D003300:Copper; D009532:Nickel