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Chemistry at the Sterically Shielded Mercury Centre of the [(η 4 ‐pp3)PtHg] Fragment
Author(s) -
Schuh Walter,
Kopacka Holger,
Wurst Klaus,
Peringer Paul
Publication year - 2001
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 - 10.1002/1099-0682(200109)2001:9<2399::aid-ejic2399>3.0.co;2-o
Subject(s) - chemistry , steric effects , mercury (programming language) , shielded cable , fragment (logic) , stereochemistry , computer science , electrical engineering , programming language , engineering
Treatment of [(η 4 ‐pp3)PtH]OTf (pp3 = tris[2‐(diphenylphosphanyl)ethyl]phosphane) with PhHgCl gave [(η 4 ‐pp3)PtHgCl]OTf ( 1a ) in good yield. The reaction of 1a with the carbonylmetallates [Mn(CO) 5 ] − or [Co(CO) 4 ] − and TlOTf produced the linear trinuclear clusters [(η 4 ‐pp3)PtHgMn(CO) 5 ]OTf ( 2 ) or [(η 4 ‐pp3)PtHgCo(CO) 4 ]OTf ( 3 ), respectively. The reaction of 1a with PR 3 and TlOTf gave [(η 4 ‐pp3)PtHg(PR 3 )](OTf) 2 ( 4 : R = n Bu; 5 : R = Ph), with Ph 2 P(CH 2 ) n PPh 2 ( n = 1, 2) or dppmSe [dppmSe = bis(diphenylphosphanyl)methane monoselenide] adducts in which the diphosphane/diphosphane monoselenide adopts a monodentate, bridging or chelating bonding mode depending on the ligand and the stoichiometry. The mercury‐bound phosphane complexes extrude elemental Hg within hours or days. The new compounds were characterised by multinuclear NMR spectroscopy and, in part, by single‐crystal X‐ray diffraction. The NMR investigations yielded unprecedented parameters, e.g. very large 31 P coordination chemical shift for a monodentate phosphane or 2 J (Hg−Pt−P) couplings that were two to three times larger than Hg−P one‐bond couplings within the same complex.