The reactions of group 14 compounds Me(n)EX(4-n) (E = Si, Ge, Sn; X =
Cl, Br, I) with electron-rich [PtMe(2)(diimine)] complexes give facile
trans oxidative addition of the E-X bond (E = Si, X = Br, I; E = Ge,
Sn, X = Cl, Br, I). The oxidative additions occur more readily for Me(
n)EX(4-n) in the sequences X = I > Br > Cl and E = Sn > Ge > Si. The f
irst stable silylplatinum(IV) complexes have been prepared in this way
, and the X-ray crystal structure of [PtIMe(2)(Me(3)Si)(bpy)] shows an
exceptionally long Pt-I bond length (2.963(1) Angstrom consistent wit
h the high traits influence of the trimethylsilyl group. H-1 NMR studi
es show that the oxidative addition involving germanium and tin reagen
ts is easily reversible. Several of the platinum(IV)-tin complexes hav
e a second molecule of tin reagent incorporated into the crystal latti
ce. The X-ray crystal structure of [PtIMe(2)(Me(3)Sn)(bpy-(t)bu(2))](2
) . Me(3)SnI-CH2Cl2 shows two distinct complexes (1:1 ratio) to be pre
sent in the unit cell. The first is the product of trans oxidative add
ition, [PtIMe(2)(Me(3)Sn)(bpy-(t)bu(2))], and the second is [PtIMe(2)(
Me(3)Sn)(bpy-tbu(2))]. Me(3)SnI. In this second complex the platinum-b
ound iodo ligand coordinates to the tin center of the Me(3)SnI molecul
e to give a trigonal-bipyramidal tin center.