REACTIVITY OF (triphos)Ni(η2-CS2) TOWARDS GROUP VIB ELEMENTS, HBF4, AND MeOSO2F. CRYSTAL STRUCTURE OF THE DITHIOCARBONATE COMPLEX Ni(S2CO)*0.5THF

Article abstract of DOI:10.1016/0022-328X(85)88012-8

The chemistry if (triphos)Ni(η²-CS2) (2) (triphos=1,1,1-tris(diphenylphosphinomethyl)ethane is compared and contrasted with that of the isostructural complex (triphos)Co(η²-CS2) (1).Reaction of 2 with O2, S8,and Se_n gives Ni(S2CO(*0.5THF (6), CH3C(CH2PPh2S)3, CH3C(CH2PPh2Se)3, respectively.Methylation of 2 by MeOSO2F, followed by addition of NaBPh4 gives <(triphos)Ni(CS2Me)>BPh4.Compounds 1 and 2 react with HBF4/diethyl ether to yield the dimers <(triphos)Co(μ-CS2)Co(triphos)>(BF4) and <(triphos)Ni(μ-S)Ni(triphos)>(BF4)2, respectively.The CS2 ligand in 2 is displaced by CO to give the carbonyl (triphos)Ni(CO).The structure of 6 has been determined from counter diffraction data.Crystal data are: a 25.937(15), b 15.560(8), c 23.186(13) Angstroem, β 92.93(5), monoclinic, space group C2/c, Z=8.The structure was solved by the heavy-atom method and refined by full-matrix least squares calculations to R=0.087 for 1464 observed reflections.The nickel atom shows a distorted square planar geometry, being surrounded by two phosphorus atoms of the triphos ligand and by the sulfur atoms of the dithiocarbonate group.