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Synthesis and Properties of Organometallic Pt II and Pt IV Complexes with Acyclic Selenoether and Telluroether Ligands and Selenoether Macrocycles
Author(s) -
Levason William,
Manning Joanna M.,
Pawelzyk Paul,
Reid Gillian
Publication year - 2006
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.200600509
Subject(s) - chemistry , denticity , octahedron , nuclear magnetic resonance spectroscopy , yield (engineering) , stereochemistry , crystallography , medicinal chemistry , organometallic chemistry , spectroscopy , crystal structure , physics , quantum mechanics , materials science , metallurgy
The first series of planar dimethyl(selenoether)Pt II complexes, [PtMe 2 L] [L = MeSe(CH 2 ) n SeMe ( n = 2 or 3), o ‐C 6 H 4 (CH 2 SeMe) 2 , [8]aneSe 2 (1,5‐diselenacyclooctane), or [16]aneSe 4 (1,5,9,13‐tetraselenacyclohexadecane)], have been obtained by treatment of [PtMe 2 (SMe 2 ) 2 ] with L in Et 2 O solution and characterised by VT 1 H, 13 C{ 1 H}, 77 Se{ 1 H} and 195 Pt{ 1 H} NMR spectroscopy, electrospray MS and microanalysis. The corresponding dimethyl(telluroether)Pt II complexes do not form under similar reaction conditions. The distorted octahedral [PtMe 3 I(L)] [L = o ‐C 6 H 4 (CH 2 SeMe) 2 , [8]aneSe 2 , [16]aneSe 4 or MeC(CH 2 SeMe) 3 ] form as stable complexes in good yield from reaction of PtMe 3 I with L in refluxing CHCl 3 and have been characterised similarly. These all show bidentate selenoether coordination, with fast pyramidal inversion occurring at room temperature. The distorted octahedral coordination environment at Pt IV is also confirmed from a crystal structure of [PtMe 3 I{ o ‐C 6 H 4 (CH 2 SeMe) 2 }]. Rare examples of (telluroether)Pt IV complexes, [PtMe 3 I{ o ‐C 6 H 4 (CH 2 TeMe) 2 }] and the dinuclear [Me 3 Pt(μ 2 ‐I) 2 (μ 2 ‐MeTeCH 2 TeMe)PtMe 3 ], have also been prepared and characterised similarly (and also by 125 Te{ 1 H} NMR spectroscopy). The [8]aneSe 2 and [16]aneSe 4 species are the first examples of alkyl Pt II or Pt IV complexes with (macro)cyclic selenoether coordination. Halide abstraction (TlPF 6 ) from [PtMe 3 I(κ 2 ‐[16]aneSe 4 )] affords [PtMe 3 (κ 3 ‐[16]aneSe 4 )]PF 6 ; a rare example of a cationic Pt IV selenoether. The (diselenoether)Pt II complexes undergo oxidative addition of MeI to yield the corresponding Pt IV species [PtMe 3 I(diselenoether)]. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)