Reactivity of the hydrido platinum(II) azide trans-PtH(N3)(PEt3)2 toward organic isocyanides and isothiocyanates: Synthesis and structures of cis-PtH(PEt3)2(CN4-2,6-Me2C6H3) and trans-Pt{S[CN4(Ph)]2}(PEt3)2

Treatments of the hydrido platinum(II) azide complex trans-PtH(N3)(PEt3)2 with organic isocyanides (CN–R) afforded trans-PtH[CN4(R)](PEt3)2 (R = 2,6-Me2C6H3 (1a) or CH2SO2–C6H4-p-Me (2)) by cycloaddition of the isocyanides into the Pt–azido bond. Complex 1a readily isomerizes to cis-PtH[CN4(R)](PEt3)2 (1b) at room temperature. The corresponding reactions with isothiocyanates (SCN–R) exclusively gave bis(tetrazole-thiolato) Pt(II) complexes, trans-Pt{S[CN4(R)]2}(PEt3)2 (R = 2,6-Me2C6H3 (3) or Ph (4)). Treatment of 1a with an equivalent of depe (1,2-bis(diethylphosphino)ethane) results in the formation of Pt(depe)2 (5).

Graphical abstractTreatments of the hydrido platinum(II) azide complex trans-PtH(N3)(PEt3)2 with organic isocyanides (CN–R) or isothiocyanates (SCN–R) afforded tetrazolato Pt(II) complexes, trans-PtH[CN4(R)](PEt3)2 or bis(tetrazole-thiolato) Pt(II) complexes, trans-Pt{S[CN4(R)]2}(PEt3)2 by cycloaddition of the isocyanides or isothiocyanates into the Pt–azido bond.Figure optionsDownload full-size imageDownload as PowerPoint slide