Synthesis and characterization of platinum(II)-thiolate complexes. Crystal and molecular structures of cis-Pt(Ph 3P) 2(SC 6H 2−2,4,6-iPr 3)Cl and cis-Pt(Ph 3P) 2(SC 6H 2−2,4,6-iPr 3) 2

Abstract

The reaction of cis-Pt(Ph 3P) 2Cl 2 with 2,4,6-triisopropylbenzenethiol (HTIPT) in benzene at 65 °C yields yellow crystals of cis-[Pt(Ph 3P) 2(TIPT)Cl] ( 1), while the reaction of cis-Pt(Ph 3P) 2Cl 2 and HTIPT in benzene at room temperature yields cis-[Pt(Ph 3P) 2(TIPT) 2] ( 2). In contrast to the tendency of solutions of [Pt(R 3P) 2(SR′) 2] complexes with sterically innocent thiolates to rearrange into a complex mixture of cis and trans complexes and polynuclear materials upon exposure to air, solutions of both 1 and 2 are stable with respect to isomerization and oligomerization. Crystal data: C 51H 50P 2SClPt·2H 2O ( 1·2H 2O), monoclinic P2 1/ c, a=16.131(5), b=18.294(3), c=17.803(6) Å, β=110.40(2)°, V=4924(2) Å 3, Z=4, D calc=1.380 g cm −1; structure solution and refinement based on 2932 reflections converged at 0.074. C 66H 76P 2S 2Pt ( 2), monoclinic P2 1/ n, a=10.854(2), b=20.639(5), c=27.080(6) Å, β=100.43(2)°, V=5966(4) Å 3, Z=4, D calc=1.325 g cm −3; structure solution and refinement based on 4550 reflections converged at 0.049.