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Halfsandwich Carbonylmetal Complexes of Vanadium, Chromium, and Manganese Containing Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane, P(C 7 H 7 ) 3
Author(s) -
Herberhold Max,
Pfeifer Andreas,
Milius Wolfgang
Publication year - 2002
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200213)628:13<2919::aid-zaac2919>3.0.co;2-7
Subject(s) - chemistry , ligand (biochemistry) , dimer , stereochemistry , crystallography , lone pair , medicinal chemistry , molecule , biochemistry , receptor , organic chemistry
The photo‐induced substitution of a CO ligand has been used to prepare the halfsandwich complexes (η 3 ‐C 3 H 5 )V(CO) 4 [P(C 7 H 7 ) 3 ] ( 1 ), (η 5 ‐C 5 H 5 )V(CO) 3 [P(C 7 H 7 ) 3 ] ( 2 ), (η 7 ‐C 7 H 7 )V(CO) 2 [P(C 7 H 7 ) 3 ] ( 3 ), (η 6 ‐C 6 H 3 Me 3 )Cr(CO) 2 [P(C 7 H 7 ) 3 ] ( 4 ), and (η 5 ‐C 5 H 5 )Mn(CO) 2 [P(C 7 H 7 ) 3 ] ( 7 ), in which the olefinic phosphane is coordinated as a conventional two‐electron ligand through the lone pair of electrons at phosphorus. Some analogues, which are permethylated at the aromatic ring ( 2* , 4* , 7* ), were included for comparison. Subsequent photo‐elimination of another CO group from 4 or 7 converts the olefinic phosphane into a chelating four‐electron ligand, leading to (η 6 ‐C 6 H 3 Me 3 )Cr(CO)[P(C 7 H 7 ) 2 (η 2 ‐C 7 H 7 )] ( 5 ) and (η 5 ‐C 5 H 5 )Mn(CO)[P(C 7 H 7 ) 2 (η 2 ‐C 7 H 7 )] ( 8 ), respectively. The η 2 ‐coordinated double bond in 5 and 8 can be displaced by trimethylphosphite to give (η 6 ‐C 6 H 3 Me 3 )Cr(CO)[P(C 7 H 7 ) 3 ][P(OMe) 3 ] ( 6 ) and (η 5 ‐C 5 H 5 )Mn(CO)[P(C 7 H 7 ) 3 ][P(OMe) 3 ] ( 9 ). The 31 P and 13 C NMR spectra of all complexes are discussed, and X‐ray structure analyses for 2 and 8 are presented. Prolonged irradiation of 7 and 8 led to a di(cycloheptatrienyl)phosphido‐bridged dimer, {(η 5 ‐C 5 H 5 )Mn(CO)[P(C 7 H 7 ) 2 ]} 2 ( 10 ).