IR Flash Kinetic Spectroscopy of C-H Bond Activation of Cyclohexane-d0 and -d12 by Cp*Rh(CO)2 in Liquid Rare Gases: Kinetics, Thermodynamics, and Unusual Isotope Effect

Schultz, Richard H.; Bengali, Ashfaq A.; Tauber, Michael J.; Wasserman, Eric; Kyle, Kevin R.; Moore, C. Bradley; Bergman, Robert G.

doi:10.1021/ja00095a047

Cited by 143 publications

(118 citation statements)

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“…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. However the IR (CO) bands of the alkane complex were not resolvable from those of the initially formed noble gas complex [38,39].…”

Section: The Role Of Organometallic Alkane Complexes In Transition Mementioning

confidence: 92%

Formation and reactivity of organometallic alkane complexes

Cowan

George

2008

Coordination Chemistry Reviews

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Section: The Role Of Organometallic Alkane Complexes In Transition Mementioning

confidence: 92%

Formation and reactivity of organometallic alkane complexes

Cowan

George

2008

Coordination Chemistry Reviews

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“…The Fe(CO) 4 radical reacts with Xe to form the Fe(CO) 4 (Xe) complex in supercritical liquid Xe solution [18]. Besides the above-mentioned noble gastransition metal carbonyl complexes, a number of noble gas-organometallic complexes such as ( 5 -C 5 H 5 )Mn(CO) 2 -(Xe), ( 5 -C 5 H 5 )M(CO) 3 (Xe) (M = Nb, Ta), Rh(CO)(PMe 3 ) 2 -(Ng) (Ng = Kr, Xe), ( 5 -C 5 H 5 )Rh(CO)(Ng) (Ng = Xe and Kr), Cp*Rh(CO)(Ng) (Cp* =  5 -C 5 Me 5 ; Ng = Xe and Kr), and Re( 5 -C 5 H 5 )(CO) 2 (Xe) have also been characterized in solution at room temperature [19][20][21][22][23][24][25][26][27]. Strong noble gas-transition metal bonding has been observed in some noble metal systems [28][29][30][31][32][33][34][35][36][37][38].…”

Section: Introductionmentioning

confidence: 99%

Are matrix isolated species really “isolated”? Infrared spectroscopic and theoretical studies of noble gas-transition metal oxide complexes

Zhao

Zhou

2010

Sci. China Chem.

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In this review, we summarize our recent results on matrix isolation infrared spectroscopic studies and theoretical investigations of noble gas-transition metal oxide complexes. The results show that some transition metal oxide species trapped in solid noble gas matrices are chemically coordinated by one or multiple noble gas atoms forming noble gas complexes and, hence, cannot be regarded as isolated species. Noble gas coordination alters the vibrational frequencies as well as the geometric and electronic structures of transition metal oxide species trapped in solid noble gas matrixes. The interactions between noble gas atoms and transition metal oxides involve ion-induced dipole interactions as well as chemical bonding interactions. Periodic trends in the bonding in these noble gas-transition metal complexes are discussed. noble gas complexes, transition metal oxides, matrix isolation, infrared spectroscopy

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“…Further ultrafast studies have demonstrated that solvation actually occurs within the first picosecond following photolysis [4,5]. Organometallic alkane complexes are proposed as intermediates in many C-H activation reactions and have been observed in mechanistic investigations of this important class of reaction [6][7][8].…”

Section: Introductionmentioning

confidence: 99%

Recent advances in organometallic alkane and noble gas complexes

Calladine

Vuong

Sun

et al. 2009

Pure and Applied Chemistry

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Fast time-resolved infrared (TRIR) spectroscopy has been useful for studying the reactions of a wide range of organometallic alkane and noble gas complexes at ambient temperature following irradiation of metal carbonyl precursor complexes. The reactivity of organometallic alkane and xenon complexes decreases both across and down groups V, VI, and VII, and for a given metal/ligand combination the alkane and xenon complexes have similar reactivities. Systematic studies of reactivity have produced long-lived Re complexes which have allowed such complexes to be characterized using NMR spectroscopy. A new approach using liquid propane at low temperature as a solvent to monitor the interaction of such weakly coordinating ligands with transition-metal centers is outlined. TRIR studies monitoring the coordination and activation of methane and ethane in supercritical methane and liquid ethane solvents at room temperature are also reviewed.

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IR Flash Kinetic Spectroscopy of C-H Bond Activation of Cyclohexane-d0 and -d12 by Cp*Rh(CO)2 in Liquid Rare Gases: Kinetics, Thermodynamics, and Unusual Isotope Effect

Cited by 143 publications

References 1 publication

Formation and reactivity of organometallic alkane complexes

Formation and reactivity of organometallic alkane complexes

Are matrix isolated species really “isolated”? Infrared spectroscopic and theoretical studies of noble gas-transition metal oxide complexes

Recent advances in organometallic alkane and noble gas complexes

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