Premium
The Preparation and Structure of [Pt(S 2 N 2 ){P(OR) n R′ 3– n } 2 ] and [Pt(SeSN 2 ){P(OMe) n Ph 3– n } 2 ] ( n = 0–3)
Author(s) -
Waddell Paul G.,
Slawin Alexandra M. Z.,
Sieffert Nicolas,
Bühl Michael,
Woollins J. Derek
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000329
Subject(s) - chemistry , chalcogen , crystallography , ligand (biochemistry) , phosphorus , nuclear magnetic resonance spectroscopy , crystal structure , dissolution , inorganic chemistry , stereochemistry , organic chemistry , biochemistry , receptor
Dissolution of [S 4 N 3 ]Cl in liquid ammonia produces a reactive solution which on treatment with cis [PtCl 2 (PR 3 ) 2 ] gives [S 2 N 2 ] 2– complexes in 32–76 % yields. Similarly, SeCl 4 and [S 4 N 3 ]Cl in a ratio of 5:1 react cleanly with cis ‐[PtCl 2 {P(OMe) n Ph 3– n }] to give the desired selenosulfur dinitrido, [SeSN 2 ] 2– complexes with no phosphorus containing starting material evident by 31 P NMR spectroscopy. The new complexes were characterised by IR, 31 P NMR, microanalysis and X‐ray crystallography with nine crystal structures being reported. In 31 P nmr the 1 J PtP coupling constants are influenced by the oxygen content of their phosphorus ligands. In the mixed chalcogen complexes the Pt–N bond lengths appear to follow a simple trend as a consequence of the electronic properties of the phosphorus ligand and these trends can be interpreted empirically by examination of the LUMO but are not well supported by DFT calculations.