D. Dakternieks,, C. Rolls
Aug 1, 1984
Citations
0
Influential Citations
7
Citations
Journal
Inorganica Chimica Acta
Abstract
Abstract Dicyclohexylphosphine, HPcycl 2 , reacts with mercury(II) and cadmium(II) halides to give isolable 1:1 adducts HgX 2 (HPcycl 2 ) (X = Cl, Br, I), CdX 2 (HPcycl 2 ) (X = Br, I) and 1:2 adducts HgX 2 (HP-cycl 2 ) 2 , CdX 2 (HPcycl) 2 (X = Cl, Br, I). The 1:2 adducts HgX 2 (HPcycl 2 ) 2 react in solution with additional HPcycl 2 to give 1:3 adducts HgX 2 (HP-cycl 2 ) 3 whereas the corresponding CdX 2 (HPcycl 2 ) 2 do not react further with HPcycl 2 .Both mercury(II) and cadmium(II) 1:1 adducts react with halide ion to give anionic [MX 3 HPcycl 2 ] − (M = Hg, Cd) species in solution. The ligand (1-(dicyclohexylphosphino))-N-phenylthioformamide, LH, (LH = (C 6 H 11 ) 2 PC(S)N(H)C 6 H 5 ) reacts with mercury(II) halides to give isolable 1:1 and 1:2 adducts, [HgX 2 (LH)] 2 and HgX 2 (LH) 2 , in which coordination of the ligand occurs only through the phosphorus atom. There is no evidence for the addition of a third LH to mercury but the 1:1 adducts react with halide ion to give anionic [HgX 3 LH] − species. The 1:2 adducts HgX 2 (HPcycl 2 ) 2 and CdX 2 (HPcycl 2 ) 2 react in solution with C 6 H 5 NCS to form the corresponding MX 2 (LH) 2 complexes. NMR data imply formation in solution of dimeric [CdX 2 (LH)] 2 compounds in which LH acts as a bridging ligand bonding through sulphur and phosphorus. Mixed ligand species HgX 2 (HPcycl 2 )(LH) and CdX 2 (HPcycl 2 )(LH) are also identified in solution. Phosphorus-31, cadmium-113 and mercury-199 NMR spectra were used to characterise new species in solution. There is no evidence for phosphido formation in any of the systems investigated in this study.