Photoisomerism of (dimethyl acetylenedicarboxylate)bis(triphenylphosphine)-platinum. Structure of (ethoxycarbonyl)((methoxycarbonyl)-acetylido)bis(triphenylphosphine)platinum(II)

Article abstract of DOI:10.1021/om00149a022

The photolysis of [Pt(PPh₃)₂(RC≡CX)] gives the acetylido complex [Pt(Ph₃P)₂R(C≡CX)] for R = X = CH₃O(CO), but similar photoisomerization does not occur for complexes of acetylenes with R = X = Ph or CH₂OH or C(CH₃)₂OH and R = H and X = CH₂OH or CO₂H or CH₂NH₂. The molecular structure of the acetylido complex [Pt(Ph₃P)₂((CO)OEt)(C≡C(CO)OCH₃)] was determined by X-ray diffraction using 6617 reflections: triclinic, P1, a = 11.069 (3) ?, b = 13.420 (3) ?, c = 14.242 (3) ?, α = 102.27 (2)°, β = 105.85 (2)°, γ = 104.01 (2)°, Z = 2. The Pt-C bond lengths are 1.991 (8) ? (to (methoxycarbonyl)acetylide) and 2.024 (8) ? (to ethoxycarbonyl), and the Pt-P bond lengths are 2.298 (2) and 2.347 (2) ?.