Intermediates in the time-resolved and matrix photochemistry of (.eta.5-cyclopentadienyl)rhodium complexes. Roles of alkane activation and rhodium-rhodium bond formation

Belt, Simon T.; Grevels, Friedrich‐Wilhelm; Klotzbuecher, Werner E.; McCamley, Andrew; Perutz, Robin N.

doi:10.1021/ja00204a008

Cited by 62 publications

(38 citation statements)

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“…The Rh center in the CpRh(CO) transient 7 absorbing at 1985 cm -1 also appears to contain a partial negative charge. The same conclusion can be reached for CpRh(CO) 2 and CpIr(CO) 2 where C-O stretching frequencies [39][40][41] are some 55 cm -1 lower than neon matrix frequencies for Rh(CO) 2 (2031 cm -1 ) and Ir(CO) 2 (2014 cm -1 ).…”

Section: Discussionsupporting

confidence: 68%

Reactions of Laser-Ablated Co, Rh, and Ir with CO: Infrared Spectra and Density Functional Calculations of the Metal Carbonyl Molecules, Cations and Anions in Solid Neon

1999

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Laser ablation produces metal atoms, cations, and electrons for reaction with CO during condensation in excess neon at 4 K. Infrared spectra are observed for the metal carbonyls, cations, and anions, which are identified from isotopic shifts ( 13 CO, C 18 O) and splittings using mixed isotopic precursors. Density functional calculations with pseudopotentials for Rh and Ir predict the observed carbonyl stretching frequencies within 1-2%. This characterization of the simple RhCO + , RhCO, and RhCO -(and Ir) species over a 350 cm -1 range provides a scale for comparison of larger catalytically active Rh and Ir carbonyl complexes in solution and on surfaces to estimate charge on the metal center. This work provides the first spectroscopic characterization of Rh and Ir carbonyl cations and anions except for the stable tetracarbonyl anions in solution.

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Section: Discussionsupporting

confidence: 68%

Reactions of Laser-Ablated Co, Rh, and Ir with CO: Infrared Spectra and Density Functional Calculations of the Metal Carbonyl Molecules, Cations and Anions in Solid Neon

1999

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“…TRIR experiments monitoring the photolysis of Rh(Cp)(CO) 2 in solution by Perutz and co-workers has characterised the unstable alkyl hydride complex, Rh(Cp)(CO)(C 6 H 11 )H, at room temperature [37]. Bergman and co-workers investigated the photolysis of Rh(Cp*)(CO) 2 in low temperature noble gas solutions, doped with alkanes, with TRIR spectroscopy and found evidence for the presence of an organometallic alkane complex as a precursor to C-H activation.…”

Section: The Role Of Organometallic Alkane Complexes In Transition Mementioning

confidence: 99%

Formation and reactivity of organometallic alkane complexes

Cowan

George

2008

Coordination Chemistry Reviews

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“…N o other strong product bands were observed immediately after photolysis, al- though weaker bands at 1963 and 2035 cm-' were noted. O n the basis of work in matrices (12) and in'liquid Kr (7,13,14), it is reasonable that the 1985 cm-' band arises from the unsolvated monocarbonyl CpRh(C0) (compound 2 in Fig. 1).…”

Section: Gas-phase Rates Of Alkane C-h Oxidative Addition To a Transimentioning

confidence: 99%

Gas-Phase Rates of Alkane C-H Oxidative Addition to a Transient CpRh(CO) Complex

Wasserman

Moore

Bergman

1992

Science

138

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The gas-phase irradiation of CpRh(CO)(2) (Cp = eta(5)-C(5)H(5)) was examined in order to study the rates of reaction of the 16-electron intermediates presumed to be involved in the C-H oxidative addition of alkanes. "Naked" (unsolvated) CpRh(CO) was detected, and direct measurements of the rates of reaction of this very short-lived complex with alkane C-H bonds were made. Activation of C-H bonds occurs on almost every collision for alkanes of moderate size, and intermediates in which the alkanes are bound to the metal centers, without their C-H bonds being fully broken, are implicated as intermediates in the overall reaction.

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Intermediates in the time-resolved and matrix photochemistry of (.eta.5-cyclopentadienyl)rhodium complexes. Roles of alkane activation and rhodium-rhodium bond formation

Cited by 62 publications

References 1 publication

Reactions of Laser-Ablated Co, Rh, and Ir with CO: Infrared Spectra and Density Functional Calculations of the Metal Carbonyl Molecules, Cations and Anions in Solid Neon

Reactions of Laser-Ablated Co, Rh, and Ir with CO: Infrared Spectra and Density Functional Calculations of the Metal Carbonyl Molecules, Cations and Anions in Solid Neon

Formation and reactivity of organometallic alkane complexes

Gas-Phase Rates of Alkane C-H Oxidative Addition to a Transient CpRh(CO) Complex

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