Reactivity of transition metal-phosphorus triple bonds towards triply bonded [{CpMo(CO)2}2]: formation of heteronuclear cluster compounds.
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].
Scheer
Manfred
M
Institut für Anorganische Chemie der Universität Regensburg, 93040 Regensburg (Germany), Fax: (+49) 941-943-4439.
Himmel
Daniel
D
Present address: Institut für Anorganische und Analytische Chemie der Albert-Ludwigs Universität Freiburg, 79104 Freiburg in Breisgau (Germany).
Kuntz
Christian
C
Institut für Anorganische Chemie der Universität Regensburg, 93040 Regensburg (Germany), Fax: (+49) 941-943-4439.
Zhan
Shuzhong
S
Present address: Department of the Applied Chemistry, South China University of Technology, Guangzhou 510640 (China).
Leiner
Eva
E
Institut für Anorganische Chemie der Universität Regensburg, 93040 Regensburg (Germany), Fax: (+49) 941-943-4439.