Bond strengths in first-row-metal carbonyl anions

Journal Article · Wed Dec 15 04:00:00 EST 1993 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00078a051· OSTI ID:7301880

Sunderlin, L S; Wang, D; Squires, R R ^[1]

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1. Purdue Univ., West Lafayette, IN (United States)

Energy-resolved collision-induced dissociation of metal carbonyl anions M(CO)[sub n][sup [minus]] (M = V, Cr, Mn, and Co) is used to determine sequential metal-carbonyl bond energies. The derived thermochemistry can be used in conjunction with literature measurements of neutral chromium carbonyl electron affinities to provide (CO)[sub n]Cr-CO bond strengths, which are compared to previous experimental determinations. Literature observations of ligand exchange reactions are used to derive other metal-ligand bond strengths. Analysis of the present data and previous values for the iron and nickel carbonyl anions shows that most metal-carbonyl ligand bond strengths are ca. 40 kcal/mol, which is apparently the intrinsic metal-carbonyl bond strength in anions. Several of the values for D[M[sup [minus]N]-2CO] are significantly lower than average; these bond strengths correlate with the energy needed to promote the metal anion into a state suitable for bonding. The electronic promotion is apparently complete after the addition of two carbonyl ligands. Comparisons of isoelectronic species confirm the general order of metal-carbonyl bond strengths, anion [>=] neutral [>=] cation. 88 refs., 6 figs., 5 tabs.

• OSTI ID: 7301880
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:25; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
99 GENERAL AND MISCELLANEOUS
990200 -- Mathematics & Computers
ANIONS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL BONDS
CHROMIUM COMPLEXES
COBALT COMPLEXES
COMPILED DATA
COMPLEXES
DATA
DISSOCIATION
INFORMATION
IONS
IRON COMPLEXES
LIGANDS
MANGANESE COMPLEXES
MATHEMATICAL MODELS
NICKEL COMPLEXES
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENT COMPLEXES
VANADIUM COMPLEXES