Dinitrogen Complexes Supported by Tris(phosphino)silyl Ligands

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The tetradentate tris(phosphino)silyl ligand [SiP(3)(iPr)] ([SiP(3)(iPr)] = [Si(o-C(6)H(4)P(i)Pr(2))(3)](-)) has been prepared, and its complexation with iron, cobalt, nickel, and iridium precursors has been explored. Several coordination complexes have been thoroughly characterized and are described. These include, for example, the divalent trigonal bipyramidal metal chlorides [SiP(3)(iPr)]M-Cl (M = Fe, Co, Ni) as well as the monovalent dinitrogen adducts [SiP(3)(iPr)]M-N(2) (M = Fe, Co, Ir), which are compared with related [SiP(3)(Ph)]M-Cl and [SiP(3)(Ph)]M-N(2) species (M = Fe, Co). Complexes of this type represent the first examples of terminal dinitrogen adducts of monovalent iron, and the ligand architecture allows examination of a unique class of dinitrogen adducts with a trans-disposed silyl donor. Oxidation of the appropriate (SiP(3)(R)]M-N(2) precursors affords the divalent iron triflate [SiP(3)(Ph)]Fe(OTf) and trivalent cobalt triflate {[SiP(3)(iPr)]Co(OTf)}{OTf} complexes, which are of interest for group transfer studies because of the presence of a labile triflate ligand. Comparative electrochemical, structural, and spectroscopic data are provided for these complexes.
Publisher
AMER CHEMICAL SOC
Issue Date
2009-03
Language
English
Article Type
Article
Keywords

SINGLE MOLYBDENUM CENTER; MONOANIONIC N2P2 LIGAND; COORDINATION CHEMISTRY; CATALYTIC-REDUCTION; NITROGEN-FIXATION; BOND ACTIVATION; IRON COMPLEXES; SPIN-STATE; FE-IVN; METAL

Citation

INORGANIC CHEMISTRY, v.48, no.6, pp.2507 - 2517

ISSN
0020-1669
DOI
10.1021/ic801855y
URI
http://hdl.handle.net/10203/97048
Appears in Collection
CH-Journal Papers(저널논문)
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