Investigation of C–C Bond Activation of sp–sp² C–C Bonds of Acetylene Derivatives via Photolysis of Pt Complexes

Abstract

Carbon−carbon bond activation reactions of acetylene derivatives featuring sp−sp 3 C−C bonds or both sp−sp 2 and sp−sp single C−C bonds were studied via photolysis of platinum compounds. Novel Pt 0 −acetylene complexes with η 2 coordination of the alkynes were synthesized and characterized.

Reactivity of platinum alkyne complexes towards N-fluorobenzenesulfonimide: formation of platinum compounds bearing a β-fluorovinyl ligand

“…The platinum-phosphorus coupling constants as well as the absorption bands for the metal-bound C-C triple bond are in accordance with the data found for the complex [Pt(PPh 3 ) 2 (PhCuCPh)] ( 1 J Pt,P = 3445 Hz, ν ˜(CuC) = 1743 cm −1 ). 73,74 Overall, complexes 1-4 might be described as platinum(0) complexes, although the bonding of the alkyne ligand involves a considerable π*backdonation.…”

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

“…By means of quantum chemical calculations, Weigand, González and co-workers investigated the first step of the mechanism of this photochemical bond activation process for a series of Pt(0)-diphenylacetylene complexes . Interestingly, the rather slow back reaction II-σ → II- π proceeds thermally at temperatures around T = 125 °C. , This reverse reaction indicates that the photochemical oxidative addition of the C­( sp )–C­( sp 2 ) bond is thermodynamically uphill. It should also be mentioned that analogous Ni(0)-diphenylacetylene complexes do not show any C–C bond activation reactions, neither photochemically nor thermally.…”

Electronic Properties of Poly‐Yne Carbon Chains and Derivatives with Transition Metal End‐Groups

“…The last three decades have witnessed a stunning collection of works devoted to the syntheses and characterizations of the redox properties, molecular and electronic structures of a variety of π‐conjugated carbon‐containing units spanning two transition metal organometallic termini Much of the interest for these so‐called molecular organometallic wires has been prompted by the rich redox chemistry of the different metal termini which encompass several transition metal elements such as, non‐exhaustively, Cr, Mn, Fe, Co, Mo, Ru, W, Re, Os, Pt, and Au organometallic fragments . Additionally, the efficiency of diverse linkers allows to convey electronic and magnetic communication between the termini.…”