Intramolecularly stabilised group 10 metal stannyl and stannylene complexes: multi-pathway synthesis and observation of platinum-to-tin alkyl transfer.

Reaction of [PdClMe(P^N)2] with SnCl2 followed by Cl-abstraction leads to apparent Pd-C bond activation, resulting in methylstannylene species trans-[PdCl{(P^N)2SnClMe}][BF4] (P^N = diaryl phosphino-N-heterocycle). In contrast, reaction of Pt analogues with SnCl2 leads to Pt-Cl bond activation, resulting in methylplatinum species trans-[PtMe{(P^N)2SnCl2}][BF4]. Over time, they isomerise to methylstannylene species, indicating that both kinetic and thermodynamic products can be isolated for Pt, whereas for Pd only methylstannylene complexes are isolated.

Coordination of a diphosphine-phosphine oxide to Au, Ag and Rh: when polyfunctionality rhymes with versatility.

Gold, silver and rhodium complexes of the diphosphine-phosphine oxide DPPO = {[o-iPr(2)P-(C(6)H(4))](2)P(O)Ph} have been prepared and characterized. Thanks to its polyfunctional character, DPPO features versatile coordination properties. According to crystallographic data, only one phosphine moiety is engaged in coordination towards (AuCl) and [RhCl(nbd)].

Original phenyl-P(O) bond cleavage at palladium(0): a combined experimental and computational study.

The reaction of the diphosphine-phosphine oxide ligand {[o-iPr(2)P-(C(6)H(4))](2)P(O)Ph} with Pd(PtBu(3))(2) proceeds with cleavage of the Ph-P(O) bond to give an original κ(P,P(O),P)-pincer complex. According to DFT calculations, this oxidative addition occurs via a three-center P,C(ipso),Pd transition state.

The [2+2] cycloaddition of alkynes at a Ru-P pi-bond.

The Ru[double bond, length as m-dash]P double bond in the 5-coordinate terminal phosphido complex [Ru(eta(5)-indenyl)(PR(2))(PPh(3))] undergoes regioselective [2+2] cycloaddition with simple and activated alkynes to give metallaphosphacyclobutene complexes. These unusual examples of alkyne insertion into a metal-heteroatom bond represent potentially important intermediates in stereoselective routes to new phosphine reagents and ligands.