Synthesis of extremely stable alkyl and hydride complexes of the type (R2NCS2)Pt(PEt3)R

Article abstract of DOI:10.1021/om00115a004

The reaction of (R₂NCS₂)Pt(PEt₃)Cl (R = Me, Et), prepared from [Pt(PEt₃)Cl₂]₂ and Na(R₂NCS₂), with alkyllithium or Grignard reagents yields (R₂NCS₂)Pt(PEt₃)(alkyl) (alkyl = Me, n-Pr, i-Pr, n-Bu, sec-Bu, i-Bu, t-Bu) complexes. These new alkylplatinum complexes are very stable and can be heated in solution at 100°C for extended periods without decomposition. The reaction of (R₂NCS₂)Pt(PEt₃)Cl with NaBH₄ yields the stable complexes (R₂NCS₂)Pt(PEt₃)H, which decompose only slowly at 110°C. This hydride (R = Me) does not react with ethylene or phenylacetylene but will react with MeO₂CC≡CCO₂Me to yield a mixture of the E and Z isomers of (Me₂NCS₂)Pt(PEt₃)(η¹-C(CO₂Me)=C(H)CO₂Me ). The reaction of (R₂NCS₂)Pt(PEt₃)Cl with AgBF₄ and ethylene yields [R₂NCS₂)Pt(PEt₃)(C₂H₄)]BF₄, but these complexes are very unstable, decomposing rapidly in the absence of ethylene.