Alessio Ghisolfi, C. Fliedel, Vitor Rosa
May 6, 2014
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0
Influential Citations
35
Citations
Journal
Organometallics
Abstract
Starting from the new ligands bis(diphenylphosphino)(N-4-(methylthio)phenyl)amine (4, N(PPh2)2(p-C6H4)SMe) and its monosulfide derivative (Ph2P)N{P(S)Ph2}(p-C6H4)SMe (4·S), we have prepared and characterized, including by X-ray crystallographic studies, their Ni(II) complexes [NiCl2{(Ph2P)2N(p-C6H4)SMe-P,P}] (5) and [NiCl2{(Ph2P)N{P(S)Ph2}(p-C6H4)SMe-P,S}] (6), respectively. The bis-sulfide compound N{P(S)Ph2}2(p-C6H4)SMe (4·S2) was also prepared and structurally characterized. Computational studies showed that the combined influence of stronger P donors and a four-membered-ring P,P chelate leads to complex 5 being thermodynamically more stable than 6, which contains one weaker P═S donor group but a five-membered P,P═S chelate ring. For comparison, the bis-chelate complex [Ni{(Ph2P)N{P(S)Ph2}(p-C6H4)SMe-P,S}2](BF4)2 (7), the monochelate complexes [NiBr2{(Ph2P)N{P(S)Ph2}(p-C6H4)SMe-P,S}] (8) and the Pd(II) analogue of 6, [PdCl2{(Ph2P)N{P(S)Ph2}(p-C6H4)SMe-P,S}] (9), were synthesized and structurally charac...