From a paramagnetic, mononuclear supersulfidonickel(II) complex to a diamagnetic dimer with a four-sulfur two-electron bond.
The first isolable "side-on" supersulfidonickel(II) complex 1(1) with the elusive S2-. ligand has been synthesized by facile oxidation of the corresponding nickel(I) precursor [LNi] with elemental sulfur. Remarkably, paramagnetic 1(1) associates voluntarily to give the diamagnetic dimer 1(2) with a four-sulfur two-electron bond as proven by X-ray diffraction analysis, spectroscopic measurements (1H NMR, EPR, SQUID), and DFT calculations. Gentle sulfur transfer of 1(1) to Ph3P or its reaction with [LNi] affords solely the genuine disulfide complex 3 having a Ni2(mu-mu2:mu2-S2) core.
Yao
Shenglai
S
Metalorganics and Inorganic Materials, Institute of Chemistry, Technische Universität Berlin, Strasse des 17, Juni 135, Sekr. C2, D-10623 Berlin, Germany.
Milsmann
Carsten
C
Bill
Eckhard
E
Wieghardt
Karl
K
Driess
Matthias
M
D019281:Dimerization; D004583:Electrons; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry*
D013455:Sulfur; D009532:Nickel; C017558:nickel sulfide