Photochemical substitution reactions of substituted Group VI metal carbonyls

Schwenzer, Gretchen M.; Darensbourg, Marcetta Y.; Darensbourg, Donald J.

doi:10.1021/ic50114a055

Cited by 38 publications

(10 citation statements)

References 2 publications

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“…Most of these studies have centered around the photolysis of parent hexacarbonyls and the nature of the species M(CO)5 generated in these reactions. The metal carbonyl complexes show photochemical substitution reaction proved earlier [38]. It has long been known that metal carbonyl compounds eliminate a CO group on photolysis in UV [39].…”

Section: Photochemically Induced Substitution Reactions Of Metal Carbmentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

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KEYWORDSThe special interest attached to the chemistry of metal carbonyls arises from several causes. While quite distinct from the metal carbonyls in the organometallic compounds, they differ in physical properties (e.g., their volatility) from all other compounds of the transition metals. Chemically, they constitute a group of compounds in which the formal valency of the metal atoms is zero, and in this respect (apart, perhaps, from the ammoniates of the alkali metals) they are comparable only with the recently discovered compounds. As a class, the carbonyls are reactive compounds, and a number of new types of inorganic compounds have been discovered. In the concepts for new products, performance, product safety, and product economy criteria are equally important. They are taken into account already when the raw material base for a new industrial product development is defined. Since the discovery of nickel carbonyl by Mond and Langer in 1888, the carbonyls of the iron group and of chromium, molybdenum and tungsten have found important technical applications, e.g., in the Mond nickel process, and for the preparation of the metals in a state of subdivision and of purity suitable for powder metallurgy, for catalysts, etc. The reaction mechanism of the processes developed for producing the carbonyls technically has only recently received its interpretations. Within the space of review it is necessary to limit discussion to a few topics. Particular stress has accordingly laid upon (a) the chemical bonding in metal carbonyls, (b) importance of IR and NMR spectroscopy in characterization of metal carbonyls, (c) substitution reactions of G-VIb metal carbonyls, (d) kinetics and mechanism of substitution reactions in metal carbonyls, (e) substituted complexes of G-VIb metal carbonyl, (f) chelate complexes of G-VIb metal carbonyls, (g) uses of G-VIb metal carbonyl complexes and (h) studies done on G-VIb metal carbonyls.

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Section: Photochemically Induced Substitution Reactions Of Metal Carbmentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

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“…In addition to the interest in (norbornadiene)M(CO)4 derivatives as catalysts in the photochemical hydrogenation process of norbornadiene, a model system for the general diene photoinduced hydrogenation in the presence of hexacarbonyls, we have been interested in the stereospecificity of photochemical substitution reactions of substituted metal carbonyl derivatives in general. [14][15] For these reasons we have examined the stereoselectivity of group 6b metal tetracarbonyl norbornadiene species toward photochemical substitution processes with l3CO as well as subsequent thermal rearrangements of some of the 13CO substituted species. This report represents a detailed presentation of our earlier communication,11 as well Journal of the American Chemical Society / 99:3 j February The numbers refer to the species which afford these absorptions as listed in Table I.…”

Section: Introductionmentioning

confidence: 99%

Photochemical substitution reactions of Group 6B metal tetracarbonyl norbornadiene complexes with carbon-13 monoxide, kinetics of subsequent thermal rearrangements in the stereospecifically labeled species, and relation of these results to the photoinduced hydrogenation process

Darensbourg¹,

Nelson²,

Murphy³

1977

J. Am. Chem. Soc.

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“…There has been considerable study of the photochemical properties of W(CO) 5 pyr and W(CO) 5 pip . A knowledge of the geometry of the excited state is important for a thorough understanding of the photochemistry; in principle the bonding changes in excited electronic states should correlate with ligand photolabilization. 1e,− Information on the structures of excited states of W(CO) 5 pyr and W(CO) 5 pip has been obtained experimentally by ground-state preresonance Raman (PRR) 4 and fast time-resolved infrared (TRIR) spectroscopy . Using a time-dependent formalism, Zink and co-workers analyzed their PRR spectra and concluded that in the lowest excited state ( 3 E) the W−N, W−C ax , and W−C eq bonds are longer than in the ground state.…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Calculations of the Geometry and Vibrational Frequencies of the Triplet State of Tungsten Pentacarbonyl Amine: A Model for the Unification of the Preresonance Raman and the Time-Resolved Infrared Experiments

1997

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Ab initio calculations of the vibrational frequencies of W(CO)5NH3 in its ground electronic 1A1 (b2 2e4) and lowest excited state 3E (b2 2e3a1 1) have been performed at the HF level. The calculated frequencies of the ν(CO) bands are in agreement with observed data on experimentally studied W(CO)5(amine) molecules. The optimized geometries of the ground and the excited states show that the W−N, W−Ceq, W−Cax, C−Oeq bonds lengthen and the C−Oax bond shortens on excitation. Our results resolve an apparent disagreement between the fast time-resolved infrared (TRIR) spectroscopy and the preresonance Raman (PRR) spectroscopy. The unexpected simultaneous lengthening of both W−Ceq and C−Oeq is due to C−Oeq antibonding character in the a1 orbital which more than offsets its loss from the e. In addition a new band, predicted but as yet unresolved in the TRIR, accounts for the C−Oax shortening as expected from the PRR W−Cax lengthening.

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Photochemical substitution reactions of substituted Group VI metal carbonyls

Abstract: Notesas methyl substitutions on the ammonium nitrogen are made. Attempts at isolating pure solutions of the glycinatochromium (III) product by ion exchange were frus-AT-04-3-326, is gratefully acknowledged.

Cited by 38 publications

References 2 publications

The chemistry of group-VIb metal carbonyls

The chemistry of group-VIb metal carbonyls

Photochemical substitution reactions of Group 6B metal tetracarbonyl norbornadiene complexes with carbon-13 monoxide, kinetics of subsequent thermal rearrangements in the stereospecifically labeled species, and relation of these results to the photoinduced hydrogenation process

Ab Initio Calculations of the Geometry and Vibrational Frequencies of the Triplet State of Tungsten Pentacarbonyl Amine: A Model for the Unification of the Preresonance Raman and the Time-Resolved Infrared Experiments

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