A study of the bonding in transition metal carbonyl hydrides

Chen, Hsiang-Wen; Jolly, William L.; Kopf, J.; Lee, Ting Ho

doi:10.1021/ja00504a017

Cited by 38 publications

(10 citation statements)

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“…Notice, however, that the sharp acidity increase following oxidation of hydride complexes is not, per se, an indication of M−H δ+ bond polarity. Experimental and theoretical studies of charge distribution in low-valent, carbonyl-based transition metal hydrides always indicate a M−H δ- bond polarization, even for highly acidic complexes. − For instance, XPS studies lead to the estimation of a hydride formal charge of −0.3, −0.8, and −0.75 for H 2 Fe(CO) 4 , HMn(CO) 5 , and HCo(CO) 4 , respectively …”

Section: Discussionmentioning

confidence: 99%

“…Experimental and theoretical studies of charge distribution in low-valent, carbonylbased transition metal hydrides always indicate a M-H δbond polarization, even for highly acidic complexes. [109][110][111] For instance, XPS studies lead to the estimation of a hydride formal charge of -0.3, -0.8, and -0.75 for H2Fe(CO)4, HMn(CO)5, and HCo(CO)4, respectively. 109 The net effect of oxidation on the M-H bond strength may thus be either a strengthening or a weakening, although strengthening is expected for M-H δsystems with very electron-rich fragments (high-energy M frontier orbital) and when the bonding energetics is dominated by the covalent component.…”

Section: Methodsmentioning

confidence: 99%

“…[109][110][111] For instance, XPS studies lead to the estimation of a hydride formal charge of -0.3, -0.8, and -0.75 for H2Fe(CO)4, HMn(CO)5, and HCo(CO)4, respectively. 109 The net effect of oxidation on the M-H bond strength may thus be either a strengthening or a weakening, although strengthening is expected for M-H δsystems with very electron-rich fragments (high-energy M frontier orbital) and when the bonding energetics is dominated by the covalent component. Compounds 1 and 2 contain ligands that have low electronegativities, are strong electron donors, and do not have strong π-accepting capabilities.…”

Section: Methodsmentioning

confidence: 99%

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Stable Paramagnetic Half-Sandwich Mo(V) and W(V) Polyhydride Complexes. Structural, Spectroscopic, Electrochemical, Theoretical, and Decomposition Mechanism Studies of [Cp*MH₃(dppe)]⁺ (M = Mo, W)

et al. 1999

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Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Stable Paramagnetic Half-Sandwich Mo(V) and W(V) Polyhydride Complexes. Structural, Spectroscopic, Electrochemical, Theoretical, and Decomposition Mechanism Studies of [Cp*MH₃(dppe)]⁺ (M = Mo, W)

et al. 1999

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“…This would seem to suggest that the hydrogen is protic. EN values tell the opposite, and so do quantum-chemical calculations in the literature [211,212]. Also Mulliken-charge calculations with the programs Caesar [24] and Gaussian [25] for HCo(CO) 4 of structure determined in ref.…”

Section: A-3 Ionic Approximation Against Brønsted-lowry Aciditymentioning

confidence: 99%

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Karen

McArdle

Takats

2014

Pure and Applied Chemistry

111

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A generic definition of oxidation state (OS) is formulated: "The OS of a bonded atom equals its charge after ionic approximation". In the ionic approximation, the atom that contributes more to the bonding molecular orbital (MO) becomes negative. This sign can also be estimated by comparing Allen electronegativities of the two bonded atoms, but this simplification carries an exception when the more electronegative atom is bonded as a Lewis acid. Two principal algorithms are outlined for OS determination of an atom in a compound; one based on composition, the other on topology. Both provide the same generic OS because both the ionic approximation and structural formula obey rules of stable electron configurations. A sufficiently simple empirical formula yields OS via the algorithm of direct ionic approximation (DIA) by these rules. The topological algorithm works on a Lewis formula (for a molecule) or a bond graph (for an extended solid) and has two variants. One assigns bonding electrons to more electronegative bond partners, the other sums an atom's formal charge with bond orders (or bond valences) of sign defined by the ionic approximation of each particular bond at the atom. A glossary of terms and auxiliary rules needed for determination of OS are provided, illustrated with examples, and the origins of ambiguous OS values are pointed out. An electrochemical OS is suggested with a nominal value equal to the average OS for atoms of the same element in a moiety that is charged or otherwise electrochemically relevant.

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“…32 The methods of synthesis and characterization of the compounds have also been described.12 Various binding energies of ligand atoms, not given in Tables I and 111 (7); CI 2p1/2 205.43 (7), 1.16 (7). F,CMn(CO)5: C 1s 296.48 (4), 1.14 (9); F 1s 692.98 (4), 1.78 (9).…”

Section: Methodsmentioning

confidence: 99%

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

Avanzino¹,

Chen²,

Donahue³

et al. 1980

Inorg. Chem.

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The Mn 2p3/*, C Is, and 0 1s binding energies of LMn(C0)5 compounds are linearly related to each other and to the inductive constant uI and the Pauling electronegativity xp of the group L. The binding energies show little correlation with the mesomeric constant uRo. Apparently only the u-donor ability of L is important in determining the degree of back-bonding to the CO groups in LMn(C0)5. The Mo 3d5/,, C Is, and 0 1s binding energies of LMO(CO)~ compounds (L = PX3 or CO) are linearly related to each other and to the phosphorus lone-pair ionization potential of the free PX3.The data indicate that both the u-donor and ?r-acceptor abilities of PX3 are important in determining the degree of back-bonding to the CO groups in X3PMo(CO)5. The *-acceptor ability of PF3 appears to be slightly greater than that of CO. IntroductionIn recent years much attention has been given to the electronic interaction of various ligands, L, with carbonyl groups in transition-metal complexes of the type L,M(CO),.l-lo No general consensus has been reached regarding the nature of the interaction. Thus, the influence of the group L on the C-O stretching force constants has been variously explainedentirely in terms of the a-acceptor character of L,3*4 entirely in terms of the a-donor character of L,5,6 and in terms of both the a-acceptor and a-donor characters of L.132*7- 9 We have used X-ray photoelectron spectroscopy to study the problem because this technique yields information not readily obtained by any other method-that is, information about the charges of individual atoms in compounds. It has been previously shown that the carbon 1s and oxygen 1s binding energies of a carbonyl group are a good measure of the d v a * back-bonding to the carbonyl group."J2 We restricted this study to volatile LM(C0)5 compounds of manganese and molybdenum and determined gas-phase core binding energies of the metal, carbon, and oxygen atoms, as well as of the atoms in the ligands L. Only three of the 20 compounds we studied have been previously studied by other workers as gases by using X-ray photoelectron spectrosco-

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A study of the bonding in transition metal carbonyl hydrides

Cited by 38 publications

References 0 publications

Stable Paramagnetic Half-Sandwich Mo(V) and W(V) Polyhydride Complexes. Structural, Spectroscopic, Electrochemical, Theoretical, and Decomposition Mechanism Studies of [Cp*MH₃(dppe)]⁺ (M = Mo, W)

Stable Paramagnetic Half-Sandwich Mo(V) and W(V) Polyhydride Complexes. Structural, Spectroscopic, Electrochemical, Theoretical, and Decomposition Mechanism Studies of [Cp*MH₃(dppe)]⁺ (M = Mo, W)

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

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

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A study of the bonding in transition metal carbonyl hydrides

Cited by 38 publications

References 0 publications

Stable Paramagnetic Half-Sandwich Mo(V) and W(V) Polyhydride Complexes. Structural, Spectroscopic, Electrochemical, Theoretical, and Decomposition Mechanism Studies of [Cp*MH3(dppe)]+ (M = Mo, W)

Stable Paramagnetic Half-Sandwich Mo(V) and W(V) Polyhydride Complexes. Structural, Spectroscopic, Electrochemical, Theoretical, and Decomposition Mechanism Studies of [Cp*MH3(dppe)]+ (M = Mo, W)

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

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

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Stable Paramagnetic Half-Sandwich Mo(V) and W(V) Polyhydride Complexes. Structural, Spectroscopic, Electrochemical, Theoretical, and Decomposition Mechanism Studies of [Cp*MH₃(dppe)]⁺ (M = Mo, W)

Stable Paramagnetic Half-Sandwich Mo(V) and W(V) Polyhydride Complexes. Structural, Spectroscopic, Electrochemical, Theoretical, and Decomposition Mechanism Studies of [Cp*MH₃(dppe)]⁺ (M = Mo, W)