title: Carbene- and carbyne-like behavior of the Mo-P multiple bond in a dimolybdenum complex inducing trigonal-pyramidal coordination of a phosphinidene ligand.
abstract: The phosphinidene complex [Mo2Cp(micro-kappa1:kappa1,eta5-PC5H4)(CO)2(eta6-R*H)] (2; Cp = eta5-C5H5; R* = 2,4,6-C6H2tBu3) has substantially different Mo-P bonds and displays a high reactivity located at the short Mo-P bond. Sideways cycloaddition or addition processes are observed toward RCCR, HCl, and [Fe2(CO)9], to give respectively metallacyclobutene and arylphosphide-bridged and heterometallic phosphinidene-bridged derivatives, a behavior reminiscent of the nucleophilic mononuclear phosphinidene complexes (carbene-like behavior), which is in good agreement with the ground-state electronic structure of 2 derived from density functional theory calculations. However, the reaction of 2 with [Co2(CO)8] implies the addition of two cobalt fragments to its short Mo-P bond and thus reveals a carbyne-like behavior of compound 2. In most of the new products, the P atom displays an unprecedented trigonal-pyramidal-like environment, instead of the expected tetrahedral distribution of bonds.
authors.affiliation: Departamento de Química OrgAnica e InorgAnica/IUQOEM, Universidad de Oviedo, Oviedo, Spain.
authors.forename: M Angeles
authors.initials: MA
authors.lastname: Alvarez
authors.forename: Inmaculada
authors.initials: I
authors.lastname: Amor
authors.forename: M Esther
authors.initials: ME
authors.lastname: García
authors.forename: Daniel
authors.initials: D
authors.lastname: García-Vivó
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Ruiz