New synthetic routes to a disulfidodinickel(II) complex: characterization and reactivity of a Ni2(mu-eta2:eta2-S2) core.
Activation of elemental sulfur by the monovalent nickel complex [PhTt (tBu)]Ni(CO) [PhTt(tBu)=phenyl{tris[(tert-butylmethyl)thio]methyl}borate] generates the disulfidodinickel(II) complex 2. This species is alternatively accessible via thermal decomposition of [PhTt (tBu)]Ni(SCPh3). Spectroscopic, magnetic, and X-ray diffraction studies establish that 2 contains a mu-eta(2):eta(2)-S2 ligand that fosters antiferromagnetic exchange coupling between the Ni (II) ions. This observation is in contrast to the lighter congener, oxygen, which strongly favors the bis(mu-oxo)dinickel(III) structure. 2 oxidizes PPh 3 to SPPh3 and reacts with O2, generating several products, one of which has been identified as [(PhTt (tBu))Ni]2(mu-S) (3).
Cho
Jaeheung
J
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
Van Heuvelen
Katherine M
KM
Yap
Glenn P A
GP
Brunold
Thomas C
TC
Riordan
Charles G
CG