Scheer, Manfred and Himmel, Daniel and Kuntz, Christian and Zhan, Shuzhong and Leiner, Eva (2008) Reactivity of Transition Metal-Phosphorus Triple Bonds towards Triply Bonded [{CpMo(CO)(2)}(2)]: Formation of Heteronuclear Cluster Compounds. CHEMISTRY-A EUROPEAN JOURNAL, 14 (29). pp. 9020-9029. ISSN 0947-6539,
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Thermolysis of [Cp*P{W(CO)(5)}(2)] (1) in the presence Of [{CpMo(CO)(2)}(2)] leads to the novel complexes [{(CO)(2)CP*W}-(CpMo(CO)(2)} (mu,eta(2):eta(1):eta(1)-P-2[W(CO)(5)}(2))] (6; Cp = eta(5)-C5H5, Cp* = eta(5)-C5Me5), [{(mu-O)(CpMoWCp*)W(CO)(4)}{mu(3)-PW(CO)(5))(2)] (7), [{CpMo(CO)(2)}(2)-{Cp*W(CO)(2)}{mu(3)-PW(CO)(5)}] (8) and [{CpMo(CO)(2)}(2){Cp*W(CO)(2)}(mu(3)-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)(2)W 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 [(mu(3)-PW(CO)(5)){CpMo(CO)(2)W(CO)(5)}] (10), in which the P atom is in a nearly trigo nal-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)(2)W P -> W(CO)(5)].
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MAIN-GROUP ELEMENTS; CRYSTAL-STRUCTURES; GROUP-15 ELEMENTS; COMPLEXES; TUNGSTEN; LIGANDS; MOLYBDENUM; OXIDATION; BEHAVIOR; ENERGY; cluster compounds; molybdenum; phosphorus; reactive intermediates; tungsten |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 11 Nov 2020 10:18 |
| Last Modified: | 11 Nov 2020 10:18 |
| URI: | https://pred.uni-regensburg.de/id/eprint/31586 |
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