872713-30-9Relevant articles and documents
Substituent effects on indium-phosphorus bonding in (4-RC6H 4S)3In·PR′3 adducts (R = H, Me, F; R′ = Et, Cy, Ph): A spectroscopic, structural, and thermal decomposition study
Briand, Glen G.,Davidson, Reagan J.,Decken, Andreas
, p. 9914 - 9920 (2008/10/09)
The tris(arylthiolate)indium(III) complexes (4-RC6H 4S)3In [R = H (5), Me (6), F (7)] were prepared from the 2:3 reaction of elemental indium and the corresponding aryl disulfide in methanol. Reaction of 5-7 with 2 equiv of the appropriate triorganylphosphine in benzene or toluene resulted in isolation of the indium-phosphine adduct series (4-RC6H4S)3In·PR′3 [R = H, R′ = Et (5a), Cy (5b), Ph (5c); R = Me, R′ = Et (6a), Cy (6b), Ph (6c); R = F, R′ = Et (7a), Cy (7b), Ph (7c)]. These compounds were characterized via elemental analysis, FT-IR, FT-Raman, solution 1H, 13C{1H}, 31P{1H}, and 19F (7a-c) NMR spectroscopy, and X-ray crystallography (5c, 6a, 6c, and 7a). NMR spectra show retention of the In-P bond in benzene-d6 solution, with phosphine 31P{1H} signals shifted downfield compared to the uncoordinated ligand. The X-ray structures show monomeric 1:1 adduct complexes in all cases. The In-P bond distance [2.5863(5)-2.6493(12) A] is influenced significantly by the phosphine substituents but is unaffected by the substituted phenylthiolate ligand. Relatively low melting points (88-130°C) are observed for all adducts, while high-temperature thermal decomposition is observed for the indium thiolate reactants 5-7. DSC/TGA and EI-MS data show a two-step thermal decomposition process, involving an initial loss of the phosphine moiety followed by loss of thiolate ligand.
