Pentacarbonylchromium-solvent complexes

Kelly, John M.; Bent, D. V.; Hermann, H; Schulte‐Frohlinde, D.; Gustorf, Ernst Koerner von

doi:10.1016/s0022-328x(00)90245-6

Cited by 76 publications

(13 citation statements)

References 9 publications

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“…Subsequent exchange of the solvent molecule with a water molecule has also been observed, 17,18 where water is a trace impurity in the solvent, which binds to the metal site more strongly than the heptane solvent used in these experiments. Photolysis of W(CO) 6 in heptane is used for demonstration here and involves key stages of a photo-activated chemical reaction (see below): (1) Initial excitation and ultrafast photodissociation (< 300 fs 20, 23 ), (2) fast (< 2 ps) solvation dynamics to form the tungsten pentacarbonyl-heptane adduct, followed by (3) vibrational cooling (> 100 ps), (4) bimolecular reaction whereby the weak heptane ligand is replaced by the stronger bonding water occurring on concentration dependent time scales (> 10 μs).…”

Section: A W(co) 6 Demonstrationmentioning

confidence: 81%

“…Solution phase M(CO) 6 (M = Cr, Mo or W) photolysis reactions and products have been well studied [17][18][19][20][21][22][23] showing loss of a CO group and solvation of the M(CO) 5 fragment to form vibrationally excited M(CO) 5 S, where S is a solvent molecule. Subsequent exchange of the solvent molecule with a water molecule has also been observed, 17,18 where water is a trace impurity in the solvent, which binds to the metal site more strongly than the heptane solvent used in these experiments.…”

Section: A W(co) 6 Demonstrationmentioning

confidence: 99%

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Time-resolved multiple probe spectroscopy

Greetham¹,

Solé²,

Clark³

et al. 2012

Review of Scientific Instruments

119

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Time-resolved multiple probe spectroscopy combines optical, electronic, and data acquisition capabilities to enable measurement of picosecond to millisecond time-resolved spectra within a single experiment, using a single activation pulse. This technology enables a wide range of dynamic processes to be studied on a single laser and sample system. The technique includes a 1 kHz pump, 10 kHz probe flash photolysis-like mode of acquisition (pump-probe-probe-probe, etc.), increasing the amount of information from each experiment. We demonstrate the capability of the instrument by measuring the photolysis of tungsten hexacarbonyl (W(CO)(6)) monitored by IR absorption spectroscopy, following picosecond vibrational cooling of product formation through to slower bimolecular diffusion reactions on the microsecond time scale.

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Section: A W(co) 6 Demonstrationmentioning

confidence: 81%

Section: A W(co) 6 Demonstrationmentioning

confidence: 99%

Time-resolved multiple probe spectroscopy

Greetham¹,

Solé²,

Clark³

et al. 2012

Review of Scientific Instruments

119

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“…However, this reaction is much slower as the rate-determining dissociation of the Cr(CO)5(solv) species (reaction 3) is approximately 107 times slower in CH3CN. 22 The Cr(SQ)3 complexes are also slowly (in 1 h) formed when quinone is added in the dark to the previously irradiated solution of Cr(CO)6 in CH3CN containing the [Cr(CO)5(CH3CN)] complex, which was spectroscopically detected (Xmax = 396 nm). This compound is only very slightly dissociated into naked Cr-(CO)5 species.…”

Section: Resultsmentioning

confidence: 99%

Redox reactivity of photogenerated pentacarbonylchromium species: formation of [Cr(III)(o-semiquinone)3] complexes

Vlček¹

1986

Inorg. Chem.

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The metal hyperfine parameters \AZ\ = 645 X 10"4 cm"1 and \ ^\ = 697 X 10"4 cm"1 of the CuF2 molecule17 are almost isotropic and far higher than those of K2Zn[Cu]F4, or almost all other copper(II) complexes, clearly implying a significant unpaired spin density in the copper 4s orbital. The gxy value of 2.601 suggests an orbital contribution µ = 0.112 for CuF2, yielding "best fit" estimates of the hyperfine constants Az = 684 X 10"4 cm"1 and Axy = 657 X 10"4 cm"1 using a value of K = -1.5. This implies an occupancy of the 4s orbital of ~33%, some 10 times that in K2Zn[Cu]F4. Simple theory suggests that the 3dza/4s mixing coefficient in tetragonally distorted complexes is proportional to the difference in metal-ligand bonding between the axial and in-plane ligands,26 so that a significantly greater 4s participation is indeed expected for the linear CuF2 molecule compared with the axially compressed CuF64" ion.Acknowledgment. The receipt of a Humboldt research fellowship to M.A.H. is gratefully acknowledged.

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“…complexes leads to extensive fragmentation, in contrast to the outcome of a photochemical experiment in condensed phase (1,(7)(8)(9)(10)(11)(12)(13)(14)(15)(16).…”

mentioning

confidence: 99%

Photofragmentation of Transition Metal Cluster Complexes in the Gas Phase

Vaida¹

1987

ACS Symposium Series

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The gas phase photofragmentation of transition metal cluster complexes is discussed. The information available for the gas phase dissociation of Mn 2 (CO) 10 , Co 3 (CO) 9 CCH 3 and Mo 2 (O 2 CCH 3 ) 4 is compared to the well established data base on cluster compounds in condensed phase. The gas phase results are discussed in light of the predictions of electronic structure theory concerning the photofragmentation of these cluster compounds.The study of metal containing compounds proved to be a difficult conceptual and technical task. To the experimentalist the difficulty comes from the fact that standard high resolution spectroscopic methods are often not applicable to the study of organometallic complexes.As experimental chemical physics added to its repertoire sensitive time and energy resolved spectroscopic probes, it opened the way for the exploration of metal containing molecules. At the same time, theoretical chemistry is developing methods able to handle many electron systems necessary for the study of transition metal complexes.The rich photochemistry of transition metal complexes has been used extensively to address questions concerning reactions of molecules in excited electronic states (1). These studies are motivated by expectations that such information will find practical application in the systematic design of organometallic reactions and catalytic processes (2^,4).To date, most of the photochemical data available for transition metal complexes comes from condensed phase studies (1). Recently, the primary photochemistry of a few model transition metal carbonyl complexes has been investigated in gas phase (5.). Studies to date indicate that there are many differences between the reactivity of organometallic species in gas phase (5,6) as compared with matrix (7-10) or solution (11-17) environments. In most cases studied, photoexcitation of isolated transition metal

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Pentacarbonylchromium-solvent complexes

Cited by 76 publications

References 9 publications

Time-resolved multiple probe spectroscopy

Time-resolved multiple probe spectroscopy

Redox reactivity of photogenerated pentacarbonylchromium species: formation of [Cr(III)(o-semiquinone)3] complexes

Photofragmentation of Transition Metal Cluster Complexes in the Gas Phase

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