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Reactivity of Transition Metal–Phosphorus Triple Bonds towards Triply Bonded [{CpMo(CO) 2 } 2 ]: Formation of Heteronuclear Cluster Compounds
Author(s) -
Scheer Manfred,
Himmel Daniel,
Kuntz Christian,
Zhan Shuzhong,
Leiner Eva
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800804
Subject(s) - chemistry , phosphinidene , heteronuclear molecule , reactivity (psychology) , crystallography , transition metal , carbon monoxide , triple bond , metal , stereochemistry , nuclear magnetic resonance spectroscopy , double bond , catalysis , organic chemistry , medicine , alternative medicine , pathology
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 }(μ,η 2 :η 1 :η 1 ‐P 2 {W(CO) 5 } 2 )] ( 6 ; Cp=η 5 ‐C 5 H 5 , Cp*=η 5 ‐C 5 Me 5 ), [{(μ‐O)(CpMoWCp*)W(CO) 4 }{μ 3 ‐PW(CO) 5 } 2 ] ( 7 ), [{CpMo(CO) 2 } 2 {Cp*W(CO) 2 }{μ 3 ‐PW(CO) 5 }] ( 8 ) and [{CpMo(CO) 2 } 2 {Cp*W(CO) 2 }(μ 3 ‐P)] ( 9 ). The structural framework of the main products 8 and 9 can be described as a tetrahedral Mo 2 WP unit that is formed by a cyclisation reaction of [{CpMo(CO) 2 } 2 ] with an [Cp*(CO) 2 WP→W(CO) 5 ] intermediate containing a WP 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 [(μ 3 ‐PW(CO) 5 ){CpMo(CO) 2 W(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) 2 WP→W(CO) 5 ].