Study of the photolysis of arenetricarbonylchromium complexes by IR, UV and 1H and 13C NMR spectroscopy

Domogatskaya, E.A.; Setkina, V. N.; Baranetskaya, N. K.; Trembovler, V.N.; Yavorskii, B. M.; Shteinshneider, A. Ya.; Petrovskii, P. V.

doi:10.1016/0022-328x(83)85022-0

Cited by 11 publications

(3 citation statements)

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“…and extends it by specifying the reduced hapticity, geometries, and energies of the complexes involved. Decomposition of (η 2 -C 6 H 6 )Cr(CO) 5 to Cr(CO) 6 is well-known and has been documented in solution and matrices. ,, As suggested by Traylor et al, this decomposition mechanism is closely related to the arene exchange reaction mechanism (exchanging CO and arene). Thus, the arene exchange reaction, taking place in the functionalization of arenes by (η 6 -arene)Cr(CO) 3 complexes, might also involve the formation of η 1 - and η 2 -arene reduced-hapticity intermediates, as found in our DFT studies.…”

Section: Discussionmentioning

confidence: 93%

“…Varied evidence for its reactivity/decomposition has been reported. Thus, in thermal reactions heated in solution or in a matrix, or for continuous photolysis in the UV range, the (η 6 -C 6 H 6 )Cr(CO) 3 complex decomposes to the Cr(CO) 6 complex. However, in gas-phase flash photolysis experiments in the UV range, transient intermediates are formed, but no significant decomposition to the Cr(CO) 6 has been reported, and regeneration of the parent complex (η 6 -C 6 H 6 )Cr(CO) 3 is observed. 13c, This suggests different mechanisms for the thermal chemistry vs the photochemistry of (η 6 -C 6 H 6 )Cr(CO) 3 .…”

Section: Discussionmentioning

confidence: 99%

“…The reactivity of (arene)Cr(CO) 3 type complexes varies as a function of the experimental conditions for the activation reaction. In general, thermochemical and steady-state photolysis , reactions result in the decomposition of (arene)Cr(CO) 3 to Cr(CO) 6 when excess CO is present. However, under most circumstances laser flash photolysis has been reported to result in the regeneration of the parent complex, (arene)Cr(CO) 3 (even when a large excess of CO is present). 13c, Both thermochemical l6,17 and photochemical 15,16 reactions, however, were suggested to involve formation of reduced-hapticity complexes.…”

Section: Introductionmentioning

confidence: 99%

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Arene Hapticity in (C₆H₆)Cr(CO)_n (n = 1−5) Complexes: A DFT Study of Singlet and Triplet Energy Surfaces

et al. 2004

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DFT calculations were employed to investigate the mechanism of formation and the interconversion of reduced-hapticity (η x -C6H6)Cr(CO) n complexes (n = 1−5, x = 1−6) on both singlet and triplet energy surfaces. A variety of functionals (mPW1k, B3LYP, B97-1, and BP86) and basis sets (SDD, SDB-cc-pVDZ, and LANL2DZ+P) were used. The same structures were consistently found for all functional/basis set combinations. The structures of the different singlet and triplet complexes and comparisons between their energies are described. On the basis of the structures and energies of the intermediates and the transition states found for singlet reduced-hapticity complexes, a mechanism for the decomposition of the (η6-C6H6)Cr(CO)3 complex to Cr(CO)6 is suggested. This mechanism, which is closely related to the arene exchange reaction mechanism, involves the formation of (η1-C6H6)Cr(CO)4 and (η2-C6H6)Cr(CO)5 complexes as ring-slippage intermediates along the pathway for the complete replacement of the benzene ring by carbonyl ligands. The barriers found for the ring-slippage process are accessible under mild conditions. Triplet reduced-hapticity complexes have different structures; however, they are similar in energy to the analogous singlet complexes. Formation of triplet reduced-hapticity complexes might take place in reactions of (η6-C6H6)Cr(CO)3 initiated by photolysis, which have been reported to show no observable decomposition to Cr(CO)6.

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Section: Discussionmentioning

confidence: 93%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Arene Hapticity in (C₆H₆)Cr(CO)_n (n = 1−5) Complexes: A DFT Study of Singlet and Triplet Energy Surfaces

et al. 2004

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Complexes in polymers: FT‐IR spectra and photochemistry of some monomeric organometallic carbonyl complexes in polystyrene, poly(methyl methacrylate), polystyrene—poly(methyl methacrylate) and polystyrene—polyacrylonitrile copolymers

Shaver

Butler

Eisenberg

et al. 1987

Applied Organom Chemis

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A convenient method for embedding organometallic complexes in polymer films has been developed and the FT-IR spectra of these films have been investigated at room temperature. Infrared data in the v(C0) stretching region are reported for M(CO), (M=Cr, Mo, W), CpMn(CO), (Cp=q5-CsH,), q-C6H6Cr(CO),L [L= co, P(n-Bu)31, ($6-C6HSNH2)Cr(C0)3, [q6-O-c~H,(NH,)M~c~(co),I, C pFe( CO) LR [L=CO, PPh,; R=Me, C(O)Me] embedded in poly(methy1 methacrylate) (PMMA), polystyrene (PS), polystyrene-poly(methy1 methacrylate) (PS-PMMA), and polystyrene-polyacrylonitrile(PS-AN) plastic films. These matrices appear to approximate the common solvents ethyl acetate, toluene, toluene-ethyl acetate, and toluene-acetonitrile, respectively, with respect to v( CO) vibrational band behavior. Several of the films have been subjected to UV irradiation and the photoproducts formed have been identified by FT-IR spectroscopy. PS-AN effectively traps photogenerated coordinatively unsaturated species via coordination of its pendant nitrile groups.

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Aryl Oligogermanes as Ligands for Transition Metal Complexes

et al. 2018

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The ligand properties of a series of aryl oligogermanes R3Ge‐GeAr3, 3–7 [Me3Ge‐GePh3 (3), Me3Ge‐Ge(pTol)3 (4), Ph3Ge‐GePh3 (5), (C6F5)3Ge‐GePh3 (6), Ph3Ge‐GeMe2GePh3 (7)] for the synthesis of transition metal carbonyl complexes such as R3Ge‐GeAr2(R′C6H4‐η6)M(CO)3 (M = Cr, 3a–7a; M = Mo, 3b; M = W, 3c) were investigated. The target complexes were obtained in moderate yields using several different synthetic approaches. The physicochemical properties of these new derivatives were investigated by IR, UV/Vis, NMR spectroscopy, electrochemistry, and DFT calculations. The molecular structures of 3c, 4a, and 5a were studied by single‐crystal X‐ray diffraction analysis. A comparative analysis of donor and acceptor properties of aryl oligogermanes as ligands for transition metal carbonyl complexes is reported.

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Study of the photolysis of arenetricarbonylchromium complexes by IR, UV and 1H and 13C NMR spectroscopy

Cited by 11 publications

References 9 publications

Arene Hapticity in (C₆H₆)Cr(CO)_n (n = 1−5) Complexes: A DFT Study of Singlet and Triplet Energy Surfaces

Arene Hapticity in (C₆H₆)Cr(CO)_n (n = 1−5) Complexes: A DFT Study of Singlet and Triplet Energy Surfaces

Complexes in polymers: FT‐IR spectra and photochemistry of some monomeric organometallic carbonyl complexes in polystyrene, poly(methyl methacrylate), polystyrene—poly(methyl methacrylate) and polystyrene—polyacrylonitrile copolymers

Aryl Oligogermanes as Ligands for Transition Metal Complexes

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Study of the photolysis of arenetricarbonylchromium complexes by IR, UV and 1H and 13C NMR spectroscopy

Cited by 11 publications

References 9 publications

Arene Hapticity in (C6H6)Cr(CO)n (n = 1−5) Complexes: A DFT Study of Singlet and Triplet Energy Surfaces

Arene Hapticity in (C6H6)Cr(CO)n (n = 1−5) Complexes: A DFT Study of Singlet and Triplet Energy Surfaces

Complexes in polymers: FT‐IR spectra and photochemistry of some monomeric organometallic carbonyl complexes in polystyrene, poly(methyl methacrylate), polystyrene—poly(methyl methacrylate) and polystyrene—polyacrylonitrile copolymers

Aryl Oligogermanes as Ligands for Transition Metal Complexes

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Arene Hapticity in (C₆H₆)Cr(CO)_n (n = 1−5) Complexes: A DFT Study of Singlet and Triplet Energy Surfaces

Arene Hapticity in (C₆H₆)Cr(CO)_n (n = 1−5) Complexes: A DFT Study of Singlet and Triplet Energy Surfaces