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Electronic interaction of ligands with carbonyl groups in transition-metal complexes of the types LMn(CO)/sub 5/ and LMo(CO)/sub 5/

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic50210a001· OSTI ID:6874483
; ; ;

The Mn 2p/sub 3/2/, C 1s, and O ls binding energies of LMn(CO)/sub 5/ compounds are linearly related to each other and to the inductive constant sigma/sub 1/ and the Pauling electronegativity x/sub p/ of the group L. The binding energies show little correlation with the mesomeric constant sigma/sub R//sup 0/. Apparently only the sigma-donor ability of L is important in determining the degree of back-bonding to the CO groups in LMn(CO)/sub 5/. The Mo3d/sub 5/2/, C 1s, and O ls binding energies of LMo(CO)/sub 5/ compounds (L = PX/sub 3/ or CO) are linearly related to each other and to the phosphorus lone-pair ionization potential of the free PX/sub 3/. The data indicate that both the sigma-donor and ..pi..-acceptor abilities of PX/sub 3/ are important in determining the degree of back-bonding to the CO groups in X/sub 3/PMo(CO)/sub 5/. The ..pi..-acceptor ability of PF/sub 3/ appears to be slightly greater than that of CO. 9 figures, 3 tables.

Research Organization:
Univ. of California, Berkeley
OSTI ID:
6874483
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 19:8; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
BINDING ENERGY
CARBON
CARBONYLS
COMPLEXES
ELECTRONEGATIVITY
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
ENERGY
FERMIONS
IONIZATION POTENTIAL
LEPTONS
LIGANDS
MANGANESE COMPLEXES
MOLYBDENUM COMPLEXES
NONMETALS
OXYGEN
PHOSPHORUS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
VALENCE
X-RAY SPECTROSCOPY