Photochemical C(<i>sp</i>)–C(<i>sp</i><sup>2</sup>) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes L<sub><i>n</i></sub>M–C≡P
Tim Görlich, Daniel S. Frost, Nico Boback, Nathan T. Coles, Birger Dittrich, Péter Müller, William D. Jones, Christian Müller
Abstract
The photochemical activation of the C(sp)–C(sp2) bond in Pt(0)-η2-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-π-complex is observed.
Topics & Concepts
ChemistryReductive eliminationCycloadditionOxidative additionArylMedicinal chemistryReactive intermediateBond cleavageStereochemistryPhotochemistryCatalysisOrganic chemistryAlkylCatalytic Alkyne ReactionsSynthesis and characterization of novel inorganic/organometallic compoundsOrganometallic Complex Synthesis and Catalysis