Synthesis, Protonation and X-ray Crystal Structures of [Ni(SC6H3Me2-2,6){triphos}]BPh4 and [Ni(SC6H4R-2){triphos}]BPh4 {R = Me, MeO Or Cl; triphos = PhP(Ph2PCH2CH2)2}: Unusual Structure when R = Cl.

The preparations of [Ni(SC₆H₃Me-2,6)(triphos)]BPh₄ and [Ni(SC₆H₄R-2)(triphos)]BPh₄ (R = Me, MeO or Cl) are described. The complexes have been characterised by ¹H and ³¹P{¹H} NMR spectroscopies, UV-visible spectroscopy and X-ray crystallography. Whilst [Ni(SC₆H₃Me-2,6)(triphos)]BPh₄ and [Ni(SC₆H₄R-2)(triphos)]BPh₄ (R = Me, MeO) contain a 4-coordinate square planar Ni, ligated by a thiolate S and three phosphorus atoms of triphos, [Ni(SC₆H₄Cl-2)(triphos)]BPh₄ is a distorted square-based pyramid due to the 2-Cl substituent being weakly bound in the apical position. The protonation of all the complexes have been studied in MeCN in situ using ³¹P{¹H} NMR spectroscopy. The protonation of these complexes with lutH⁺ (lut = 2,6-dimethylpyridine) indicate simple protonation of the thiolate S. However, protonation by picH+ (pic = 4-methylpyridine) indicate that both protonation and displacement of the thiolate occurs. [ABSTRACT FROM AUTHOR]