title: Reactivity of transition metal-phosphorus triple bonds towards triply bonded [{CpMo(CO)2}2]: formation of heteronuclear cluster compounds.
abstract: Thermolysis of [Cp*P{W(CO)5}2] (1) in the presence of [{CpMo(CO)2}2] leads to the novel complexes [{(CO)2Cp*W}{CpMo(CO)2}(micro,eta2:eta1:eta1-P2{W(CO)5}2)] (6; Cp=eta5-C5H5, Cp*=eta5-C5Me5), [{(micro-O)(CpMoWCp*)W(CO)4}{micro3-PW(CO)5}2] (7), [{CpMo(CO)2}2{Cp*W(CO)2}{micro3-PW(CO)5}] (8) and [{CpMo(CO)2}2{Cp*W(CO)2}(micro3-P)] (9). The structural framework of the main products 8 and 9 can be described as a tetrahedral Mo2WP unit that is formed by a cyclisation reaction of [{CpMo(CO)2}2] with an [Cp*(CO)2W[triple chemical bond]P-->W(CO)5] intermediate containing a W--P triple bond and subsequent metal-metal and metal-phosphorus bond formation. Photolysis of 1 in the presence of [{CpMo(CO)2}2] gives 8, 9 and phosphinidene complex [(micro3-PW(CO)5){CpMo(CO)2W(CO)5}] (10), in which the P atom is in a nearly trigonal-planar coordination environment formed by one {CpMo(CO)2} and two {W(CO)5} units. Comprehensive structural and spectroscopic data are given for the products. The reaction pathways are discussed for both activation procedures, and DFT calculations reveal the structures with minimum energy along the stepwise Cp* migration process under formation of the intermediate [Cp*(CO)2W[triple chemical bond]P-->W(CO)5].
authors.affiliation: Institut für Anorganische Chemie der Universität Regensburg, 93040 Regensburg (Germany), Fax: (+49) 941-943-4439.
authors.forename: Manfred
authors.initials: M
authors.lastname: Scheer
authors.affiliation: Present address: Institut für Anorganische und Analytische Chemie der Albert-Ludwigs Universität Freiburg, 79104 Freiburg in Breisgau (Germany).
authors.forename: Daniel
authors.initials: D
authors.lastname: Himmel
authors.affiliation: Institut für Anorganische Chemie der Universität Regensburg, 93040 Regensburg (Germany), Fax: (+49) 941-943-4439.
authors.forename: Christian
authors.initials: C
authors.lastname: Kuntz
authors.affiliation: Present address: Department of the Applied Chemistry, South China University of Technology, Guangzhou 510640 (China).
authors.forename: Shuzhong
authors.initials: S
authors.lastname: Zhan
authors.affiliation: Institut für Anorganische Chemie der Universität Regensburg, 93040 Regensburg (Germany), Fax: (+49) 941-943-4439.
authors.forename: Eva
authors.initials: E
authors.lastname: Leiner