Photochemistry of phosphine hydride complexes of iron group metals

Bergamini, Paola; Sostero, Silvana; Traverso, O.

doi:10.1016/0022-328x(86)84045-1

Cited by 16 publications

(24 citation statements)

References 7 publications

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“…This phenomenon was previously observed with cis ‐(dppe) 2 FeH 2 , which formed (dppe)FeH( o ‐C 6 H 4 PPhCH 2 CH 2 PPh 2 ) upon UV or visible light irradiation ,,. The dppe structure could be restored by mixing the ortho ‐metalated complex with H 2 (at 52–70 °C), HX (X=Cl, RC≡C), and a coordinating ligand L (L=ethylene, CO, MeCN), which yielded cis ‐(dppe) 2 FeH 2 , (dppe) 2 FeHX, and (dppe) 2 FeL, respectively ,,,…”

Section: Bidentate Ligand Systemssupporting

confidence: 74%

“…The last two formed oxidative addition products cis ‐(dmpe) 2 FeH 2 and (dmpe) 2 Fe(CN){C(CN)=C(CN) 2 }. Photolysis of cis ‐(dppe) 2 FeH 2 in the presence of CO and tetracyanoethylene also produced (dppe) 2 Fe(CO) and (dppe) 2 Fe(CN){C(CN)=C(CN) 2 } . Upon mixing with I 2 (in solid or solution form), cis ‐(dppe) 2 FeH 2 was readily converted to (dppe)FeI 2 accompanied by H 2 evolution ,.…”

Section: Bidentate Ligand Systemsmentioning

confidence: 99%

“…Elimination of H 2 from (diphosphine) 2 FeH 2 under photochemical or thermal conditions allowed these dihydrides to serve as precursors to coordinatively unsaturated Fe(0) species. Photolysis of cis ‐(dmpe) 2 FeH 2 was shown to generate (dmpe) 2 Fe as a transient, highly reactive intermediate,, which could trap a variety of compounds including CO, N 2 , ethylene, H 2 , and tetracyanoethylene. The last two formed oxidative addition products cis ‐(dmpe) 2 FeH 2 and (dmpe) 2 Fe(CN){C(CN)=C(CN) 2 }.…”

Section: Bidentate Ligand Systemsmentioning

confidence: 99%

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Iron Dihydride Complexes: Synthesis, Reactivity, and Catalytic Applications

Dai

Guan

2017

Israel Journal of Chemistry

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Iron dihydride complexes often play important roles in catalytic reactions that employ reducing agents such as H 2 , boranes, and silanes. Development of more efficient and selective iron-based catalysts for these processes requires effective synthetic strategies and a deeper understanding of the reactivity of the dihydride complexes. The purpose of this review is to provide the readers with an overview of different ligand systems that have been used to support iron dihydride complexes. Figure 1. General reactivity of cis-and trans-FeH 2 beneficial to catalytic reduction.

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Section: Bidentate Ligand Systemssupporting

confidence: 74%

Section: Bidentate Ligand Systemsmentioning

confidence: 99%

Section: Bidentate Ligand Systemsmentioning

confidence: 99%

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Iron Dihydride Complexes: Synthesis, Reactivity, and Catalytic Applications

Dai

Guan

2017

Israel Journal of Chemistry

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“…3% HD. A similar quantity of HD is formed in a crossover experiment where Ru(H) 2 (dmpe) 2 and Ru(D) 2 (dmpe) 2 are irradiated together (313 nm) in solution . Photolysis in an EPR spectrometer at low temperature in the presence of a spin trap also failed to generate a hydrogen spin adduct.…”

Section: Photochemical Processesmentioning

confidence: 83%

“…Irradiation in benzene solution in the presence of carbon monoxide or ethylene led to loss of H 2 and the formation of the corresponding complexes Ru(dmpe) 2 L or Ru(dppe) 2 L (L = CO, C 2 H 4 ). In the absence of substrate, the products were identified as Ru 2 (dmpe) 5 and RuH(C 6 H 4 PPhCH 2 CH 2 PPh 2 )(dppe), respectively . In understanding these reactions, it is important to note that the cis -dihydride isomers dominate over the trans isomers (Ru(H) 2 (dmpe) 2 ca.…”

Section: Photochemical Processesmentioning

confidence: 99%

Photochemistry of Transition Metal Hydrides

2016

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Photochemical reactivity associated with metal-hydrogen bonds is widespread among metal hydride complexes and has played a critical part in opening up C-H bond activation. It has been exploited to design different types of photocatalytic reactions and to obtain NMR spectra of dilute solutions with a single pulse of an NMR spectrometer. Because photolysis can be performed on fast time scales and at low temperature, metal-hydride photochemistry has enabled determination of the molecular structure and rates of reaction of highly reactive intermediates. We identify five characteristic photoprocesses of metal monohydride complexes associated with the M-H bond, of which the most widespread are M-H homolysis and R-H reductive elimination. For metal dihydride complexes, the dominant photoprocess is reductive elimination of H2. Dihydrogen complexes typically lose H2 photochemically. The majority of photochemical reactions are likely to be dissociative, but hydride complexes may be designed with equilibrated excited states that undergo different photochemical reactions, including proton transfer or hydride transfer. The photochemical mechanisms of a few reactions have been analyzed by computational methods, including quantum dynamics. A section on specialist methods (time-resolved spectroscopy, matrix isolation, NMR, and computational methods) and a survey of transition metal hydride photochemistry organized by transition metal group complete the Review.

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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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Photochemistry of phosphine hydride complexes of iron group metals

Cited by 16 publications

References 7 publications

Iron Dihydride Complexes: Synthesis, Reactivity, and Catalytic Applications

Iron Dihydride Complexes: Synthesis, Reactivity, and Catalytic Applications

Photochemistry of Transition Metal Hydrides

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.

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