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Phosphinidene Transition Metal Complexes: A Combined Ab Initio MO‐DFT Study of Cr(CO) 5 –PR
Author(s) -
Creve Steven,
Pierloot Kristine,
Nguyen Minh Tho,
Vanquickenborne Luc G.
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199901)1999:1<107::aid-ejic107>3.0.co;2-4
Subject(s) - chemistry , phosphinidene , singlet state , ab initio , crystallography , transition metal , ground state , metal , ab initio quantum chemistry methods , ligand (biochemistry) , density functional theory , computational chemistry , molecule , photochemistry , excited state , catalysis , atomic physics , biochemistry , physics , receptor , organic chemistry
Ab initio MO and DFT calculations have been performed on phosphinidene complexes of the type Cr(CO) 5 –PR, with R = H, CH 3 , SiH 3 , NH 2 , PH 2 , OH, and SH. The formation of the Cr–P bond essentially arises from a ligand‐to‐metal charge transfer. While a significant π backdonation is also observed for the Cr(CO) 5 –PH, Cr(CO) 5 –PCH 3 , and Cr(CO) 5 –PSiH 3 complexes, this is less the case for Cr(CO) 5 –POH, Cr(CO) 5 –PSH, and Cr(CO) 5 –PNH 2 , and the backbonding almost disappears for Cr(CO) 5 –PPH 2 . In both the lowest lying singlet and triplet states, all complexes exhibit a staggered conformation. CASSCF/CASPT2 calculations performed with the ANO basis sets indicate a closed‐shell singlet ground state along the whole series. The binding energy between Cr(CO) 5 and PR ranges from 216 kJ/mol for Cr(CO) 5 –PNH 2 to 127 kJ/mol for Cr(CO) 5 –PSiH 3 (B3LYP values). In general, the B3LYP‐DFT scheme yields reasonable qualitative and quantitative results when compared with CASPT2(12/12).