Insertion of Elemental Sulfur and SO₂ into the Metal−Hydride and Metal−Carbon Bonds of Platinum Compounds

Abstract

Elemental sulfur (S8) has been found to insert only one sulfur atom into the metal−hydride bonds of the platinum alkyl and aryl hydride complexes [(dcpe)PtRH] (dcpe = Cy2PC2H4PCy2). Unlike the parent compounds, the S-inserted complexes do not undergo reductive elimination to form the corresponding alkane- or arenethiols. Methane is lost from the methyl sulfhydryl complex. Sulfur dioxide was also found to insert into a platinum−methyl bond to form the corresponding S-bound sulfinate, which upon reacting with mineral acids generates methylsulfinic acid.

The insertion of sulfur dioxide into palladium–methyl bonds: the synthesis and X-ray crystal structure of an unusual [(dppp)PdOS(Me)O]2[BAr′4]2 dimer

“…This is in contrast to observations by Jones for analogous L 2 PtMe 2 complexes which readily insert SO 2 via a five coordinate intermediate. 8 We have also carried out the analogous reaction of Pd complex 6 with SO 2 to form 7 presumably also via a five coordinate intermediate [eqn. (1)].…”

“…2-3 where resonances for an -S(O) 2 CH 3 group would be expected. 8 A preparative scale reaction † was carried out in an attempt to isolate single crystals. Indeed, pale yellow crystals suitable for X-ray diffraction were isolated after recrystallisation of the crude product from dichloromethane-hexanes at 230 °C.…”

New Platinum(II) Complex Containing Asymmetric Tetra Dentate Schiff Base Ligand Synthesis, Characterization and DFT Calculation

“…As an example, the C(1)-O(1) ,S(1)-C(5) and S(1)-C(6) bond distances in ligand calculated as 1.353 Å, 1.891 Å and 1.89 Å respectively, but changed to 1.316 Å, 1.87 Å, 1.86 Å in the complex. In the complex [Pt(pytaO 2 Nsal)]Cl, Pt-O ( 101 -(1 ( 101 ) and Pt-N(2) ( 186 ) bond lengths slightly longer than related Schiff base complex [14][15][16][17][18][19] (Table 1). The absorption bands at 3446, 1284.5, 678,1652, 1606 cm -1 in the IR spectrum of ligand are a ribu ed o ν(O-H phenolic ν(C-O phenolic ), ν(C-S ν(C= pyridinic ), ν(C= iminic ) respectively.…”

Synthesis and reactivity of platinacycloalkanes

“…Very little work has been reported in the literature on the insertion of elemental sulfur (S 8 ) into transition metal-carbon bonds [32]. Some nickel(II)-thiolate complexes obtained from insertion of sulfur have been reported [33].…”