Photochemical C(sp)-C(sp2) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes LnM-CP

The photochemical activation of the C(sp)-C(sp(2)) bond in Pt(0)-eta(2)-aryl-phosphaalkyne complexes leads selectively to coordination compounds of the type LnPt(aryl)(C P). The oxidative addition reaction is a novel, clean, and atom-economic route for the synthesis of reactive terminal Pt(II)-cyaphido complexes, which can undergo [3 + 2] cycloaddition reactions with organic azides, yielding the corresponding Pt(II)-triazaphospholato complexes. The C-C bond cleavage reaction is thermodynamically uphill. Upon heating, the reverse and quantitative reductive elimination toward the Pt(0)-phosphaalkyne-pi-complex is observed.

Automated summary

The photochemical activation selectively leads to the formation of coordination compounds of the type LnPt(aryl)(C P) in Pt(0)-eta(2)-aryl-phosphaalkyne complexes, and the subsequent oxidative addition reaction is a novel and clean route for the synthesis of reactive terminal Pt(II)-cyaphido complexes. The thermodynamically uphill C-C bond cleavage reaction can be reversed upon heating, leading to quantitative reductive elimination towards the Pt(0)-phosphaalkyne-pi-complex.