Issue 2, 2001

Distorted square planar nickel(II) carbonyl complexes containing terminal thiolate/selenolate ligands

Abstract

Distorted square planar [Ni(CO)(SR)n(SePh)3 − n] (n = 0 (1), 3 (2), 1 (3) or 2 (4); R = Ph or C4H3S) complexes, were prepared by unique Cp/PhS (PhSe) exchange reactions and oxidative addition. (SC4H3S)2, [NiCp(CO)]2 and 2 equivalents of fac-[N(PPh3)2][Fe(CO)3(SC4H3S)3] in thf led to the isolation of [N(PPh3)2][Ni(CO)(SC4H3S)3] and [FeCp(CO)2(SC4H3S)]. Complex [Ni0(CO)3(SePh)] was obtained upon chemical reduction of complex [NiII(CO)(SePh)3] with [BH4] under a CO atmosphere in thf. [NiII(CO)(SePh)3] was reobtained upon oxidative addition of diphenyl diselenide and benzeneselenol to [Ni0(CO)3(SePh)] in thf. The mixed-chalcogenolate nickel(II) carbonyl complexes [Ni(CO)(SPh)n(SePh)3 − n] (n = 1 or 2) were prepared by PhSe/PhS ligand exchange reaction and oxidative addition of diphenyl disulfide to [Ni(CO)3(SePh)] individually. Complexes [NiII(CO)(SePh)3], [NiII(SC5H4N)3], [Ni0(CO)3(SC5H4N)] and [Ni0(CO)3(SePh)] are chemically interconvertible at ambient temperature. Coordinative addition of the metalloanion [Mn(CO)5] ([Fe(CO)4(SePh)]) to complex [Ni(CO)(SePh)3] and subsequent redox under a CO atmosphere led to formation of cis-[Mn(CO)4(SePh)2] (fac-[Fe(CO)3(SePh)3]) and [Ni0(CO)3(SePh)]. Nickel(II)/nickel(0) carbonyl thiolate complexes are more unstable thermally than the corresponding carbonyl selenolate complexes. Isotopic shift experiments demonstrate the lability of carbonyl ligand(s) of complexes 1–4 and [Ni(CO)3(SePh)] species. The vibrational spectroscopy of the NiII(CO) fragment (ν(CO) ranges from 2023 to 2043 cm−1) found in 1–4 may be regarded as a spectroscopic reference for the carbonyl binding site of [NiFe] hydrogenases and CO dehydrogenase.

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Supplementary files

Article information

Article type
Paper
Submitted
07 Nov 2000
Accepted
14 Nov 2000
First published
21 Dec 2000

J. Chem. Soc., Dalton Trans., 2001, 138-143

Distorted square planar nickel(II) carbonyl complexes containing terminal thiolate/selenolate ligands

W. Liaw, C. Chen, C. Lee, G. Lee and S. Peng, J. Chem. Soc., Dalton Trans., 2001, 138 DOI: 10.1039/B008902H

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