Quantifying the trans influence of triphenylarsine. Crystal and molecular structures of cis-[PtCl 2(SMe 2)(AsPh 3)] and cis-[PtCl 2(AsPh 3) 2]·CHCl 3

Abstract

Reaction between a mixture of cis– trans-[PtCl 2(SMe 2) 2] and 1 equiv. AsPh 3 in chloroform gives cis-[PtCl 2(SMe 2)(AsPh 3)] crystallizing in P2 1/ n with a=10.397(2), b=14.876(3), c=13.956(3) Å, β=90.86(3)° and Z=4. Selected geometrical parameters are PtAs 2.3531(10), PtS 2.262(2), PtCl ( trans to S) 2.301(2), PtCl ( trans to As) 2.328(2) Å and SPtAs 88.85(6), SPtCl(2) 90.77(8), AsPtCl(1) 91.07(6) and ClPtCl 89.42(7)°. cis-[PtCl 2(AsPh 3) 2]·CHCl 3 crystallizes in P2 1/ c with a=20.557(4), b=9.5951(19), c=20.147(4) Å, β=96.77(3)° and Z=4. Selected geometrical parameters are PtAs(1) 2.3599(9), PtAs(2) 2.3770(9), PtCl(1) ( trans to As(1)) 2.3515(18), PtCl(2) ( trans to As(2)) 2.3251(18) Å and AsPtAs 97.87(3), As(1)PtCl(2) 88.67(5), As(2)PtCl(1) 84.30(5) and ClPtCl 89.32(7)°. By comparison with related structures from the literature the following trans influence series was established PMe 2Ph>PPh 3>AsPh 3≈SbPh 3>Me 2SO≈SMe 2≈SPh 2>NH 3≈olefin>Cl −>MeCN.