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Phosphinomethyl complexes of zirconium: A molecular orbital study of structure, bonding and reactivity problems
Author(s) -
Hofmann Peter,
Stauffert Peter,
Schore Neil E.
Publication year - 1982
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19821150612
Subject(s) - chemistry , heterolysis , denticity , ligand (biochemistry) , crystal structure , crystallography , zirconium , molecular orbital , reactivity (psychology) , stereochemistry , electronic structure , molecule , computational chemistry , inorganic chemistry , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology , catalysis
The electronic structure and geometry of bent sandwich phosphinomethyl complexes of Zr IV and Zr III have been investigated by means of molecular orbital calculations. A fragment MO approach and perturbation arguments are utilized to explain the unusual experimental structure of Cp 2 ZrCl(CH 2 PPh 2 ) ( 1 ). Various factors influencing monodentate (η 1 ) vs. bidentate (η 2 ) ligand coordination of a phosphinomethyl ligand in zirconocene derivatives are analyzed, allowing to extrapolate to other Cp 2 M(X)() systems (: potentially mono‐ or bidentate ligand) in general. Structural and chemical consequences of one electron reduction of 1 are interpreted on the basis of the MO calculations. is shown to possess an η 1 ‐phosphinomethyl ligand and to be unstable towards heterolytic loss of Cl − or CH 2 PPh 2 − . The ground state structure of d 1 ‐Cp 2 Zr(CH 2 PPh 2 ) is calculated to contain an η 2 ‐phosphinomethyl group, consistent with the observed ESR spectrum of the reduction product of 1 .