334543-45-2Relevant academic research and scientific papers
Distorted square planar nickel(II) carbonyl complexes containing terminal thiolate/selenolate ligands
Liaw, Wen-Feng,Chen, Chien-Hong,Lee, Chien-Ming,Lee, Gene-Hsiang,Peng, Shie-Ming
, p. 138 - 143 (2007/10/03)
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(SC4 H3S)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(IIl)/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 (v(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. The Royal Society of Chemistry 2001.
