Organometallic photochemistry in supercritical fluids: Reactions of cyclopentadienyl carbonyl and phosphine carbonyl complexes of manganese with dinitrogen

Banister, James A.; George, Michael W.; Grubert, Stefanie; Howdle, Steven M.; Jobling, Margaret; Johnson, Frank P. A.; Morrison, Sara L.; Poliakoff, Martyn; Schubert, Ulrich; Westwell, Jeremy R.

doi:10.1016/0022-328x(94)87196-5

Cited by 22 publications

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“…In this spectrum, J HH corresponds to the peak separation of the antiphase features, while the other splittings arise from coupling to 31 (2). In contrast to the measurements described above, the steady-state photolysis of an optically dilute solution of 1 under a p-H 2 atmosphere at 295 K in benzene-d 6 or toluene-d 8 undertaken either ex situ (λ >290 nm) or in situ with a laser (λ 325 nm, cw) resulted in no change in the observed NMR spectra of these solutions and PHIP was no longer observed in the hydride resonances of 1.…”

Section: ■ Resultsmentioning

confidence: 99%

“…H} NMR spectrum now displayed two new singlets at δ −6.0 and 59.4 in addition to the resonances of 1. The new 31 …”

Section: ■ Resultsmentioning

confidence: 99%

“…As complex 2 disappeared, the signals for 1 and a new hydride resonance started to grow in a thermal reaction. This new product signal appears at δ −6.34, as a triplet with J = 23 Hz, that connects to a single 31 …”

Section: H{mentioning

confidence: 99%

“…1 H} resonance at δ 57.1 and simplifies into a singlet upon 31 46 The exchange was postulated to occur via a trigonal twist mechanism, but alternative mechanisms involving dihydrogen isomers are also possible (see Discussion). We undertook a series of 1D EXSY experiments to probe for the thermal exchange of 1 with free H 2 or free PPh 3 .…”

Section: P{mentioning

confidence: 99%

“…These peaks are split into triplets of antiphase doublets, in an overall 1:1 intensity ratio, in the 1 H NMR spectrum and simplify into antiphase doublets upon 31 P decoupling. The triplet splitting is due to coupling to two equivalent 31 P nuclei that lie cis to the hydrides (δ −6.28, J PH = 30 Hz; δ −9.46, J PH = 26 Hz). We therefore assign 3 to Ru(H) 2 (AsPh 3 )(CO)(PPh 3 ) 2 , formed by PPh 3 loss and AsPh 3 coordination, with the geometry shown in Scheme 3.…”

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confidence: 99%

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Competing Pathways in the Photochemistry of Ru(H)₂(CO)(PPh₃)₃

et al. 2018

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Article:Procacci, Barbara orcid.org/0000-0001-7044-0560, Duckett, Simon B. orcid.org/0000-0002-9788-6615, George, Michael W. et al. (6 more and with pyridine on a nanosecond time scale. These two pathways, reductive elimination of H 2 and PPh 3 loss, are shown to occur with approximately equal quantum yields upon 355 nm irradiation. Low-temperature photolysis in the presence of H 2 reveals the formation of the dihydrogen complex Ru(H) 2 (η 2 -H 2 )(CO)(PPh 3 ) 2 , which is detected by NMR and IR spectroscopy. This complex reacts further within seconds at room temperature, and its behavior provides a rationale to explain the PHIP results. Furthermore, photolysis in the presence of AsPh 3 and H 2 generates Ru(H) 2 (AsPh 3 )(CO)(PPh 3 ) 2 . Two isomers of Ru(H) 2 (CO)(PPh 3 ) 2 (pyridine) are formed according to NMR spectroscopy on initial photolysis of 1 in the presence of pyridine under H 2 . Two further isomers are formed as minor products; the configuration of each isomer was identified by NMR spectroscopy. Laser pump-NMR probe spectroscopy was used to observe coherent oscillations in the magnetization of one of the isomers of the pyridine complex; the oscillation frequency corresponds to the difference in chemical shift between the hydride resonances. Pyridine substitution products were also detected by TRIR spectroscopy.

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Section: ■ Resultsmentioning

confidence: 99%

“…H} NMR spectrum now displayed two new singlets at δ −6.0 and 59.4 in addition to the resonances of 1. The new 31 …”

Section: ■ Resultsmentioning

confidence: 99%

Section: H{mentioning

confidence: 99%

Section: P{mentioning

confidence: 99%

mentioning

confidence: 99%

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Competing Pathways in the Photochemistry of Ru(H)₂(CO)(PPh₃)₃

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Photochemistry of Transition Metal ComplexesBased in part on the article Photochemistry of Transition Metal Complexes by Lisa McElwee‐White which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Bitterwolf¹

2005

Encyclopedia of Inorganic Chemistry

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Photochemistry has evolved into a powerful tool for the highly selective generation of reactive intermediates in inorganic and organometallic chemistry. This review examines the state of the art in the examination of mechanisms of photochemical reactions utilizing techniques such as frozen matrices and fast time‐resolved methods. The application of photochemistry to the preparation of dihydrogen, alkane, and noble gas intermediates is reviewed along with the significance of these intermediates in the understanding of the mechanism of oxidative addition processes. Experiment and theory of charge transfer phenomena are extensively discussed along with the application of these processes to semiconductor and biochemical studies. Applications of photocrystallography to the examination of linkage isomers and very short‐lived excited state species are reviewed. Finally, a number of examples of the application of photochemical reactions, such as the photolysis of Fisher carbene species to generate ketenelike intermediates, to synthesis are discussed. The literature is reviewed to the end of 2003.

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Influence of an Additional Gas on the Hydroformylation and Related Reactions

Bianchi

Frediani

Piacenti

et al. 2002

Eur. J. Inorg. Chem.

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The initial rate of the catalytic carbonylations reported in this paper [the hydroformylation of olefins in the presence of Co 2 (CO) 8 , the carbonylation of orthoesters catalyzed by Co 2 (CO) 8 ], and the formation of tetracarbonylhydridocobalt(I) from octacarbonyldicobalt and dihydrogen] was reduced by the addition of dinitrogen, argon, or xenon. The influence of xenon on the rate of hydroformylation was greater than that of dinitrogen or argon. Helium and neon,

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Organometallic photochemistry in supercritical fluids: Reactions of cyclopentadienyl carbonyl and phosphine carbonyl complexes of manganese with dinitrogen

Cited by 22 publications

References 16 publications

Competing Pathways in the Photochemistry of Ru(H)₂(CO)(PPh₃)₃

Competing Pathways in the Photochemistry of Ru(H)₂(CO)(PPh₃)₃

Photochemistry of Transition Metal ComplexesBased in part on the article Photochemistry of Transition Metal Complexes by Lisa McElwee‐White which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Influence of an Additional Gas on the Hydroformylation and Related Reactions

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Organometallic photochemistry in supercritical fluids: Reactions of cyclopentadienyl carbonyl and phosphine carbonyl complexes of manganese with dinitrogen

Cited by 22 publications

References 16 publications

Competing Pathways in the Photochemistry of Ru(H)2(CO)(PPh3)3

Competing Pathways in the Photochemistry of Ru(H)2(CO)(PPh3)3

Photochemistry of Transition Metal ComplexesBased in part on the article Photochemistry of Transition Metal Complexes by Lisa McElwee‐White which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Influence of an Additional Gas on the Hydroformylation and Related Reactions

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Competing Pathways in the Photochemistry of Ru(H)₂(CO)(PPh₃)₃

Competing Pathways in the Photochemistry of Ru(H)₂(CO)(PPh₃)₃