Synthesis and reactivity of [2]disilaniobocenophanes

Braunschweig, Holger; Gross, M.; Kraft, Katharina

doi:10.1016/j.jorganchem.2010.09.027

Cited by 4 publications

(3 citation statements)

References 53 publications

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“…More recently the complex {(Me 2 Si) 2 (η 5 -C 5 H 4 ) 2 }Nb(H) 3 was prepared and found to be very unstable both in solution and in solid state. However, irradiation in benzene- d 6 converted it to the dimeric analogue [(Me 2 Si) 2 {μ-(η 1 :η 5 -C 5 H 3 )}(η 5 -C 5 H 4 )NbH] 2 ; H 2 photoelimination was proposed as the primary photoprocess …”

Section: Metal Hydride Photochemistry By Transition Metal Groupmentioning

confidence: 99%

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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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Section: Metal Hydride Photochemistry By Transition Metal Groupmentioning

confidence: 99%

“…However, irradiation in benzene-d 6 converted it to the dimeric analogue [(Me 2 Si) 2 {μ-(η 1 :η 5 -C 5 H 3 )}(η 5 -C 5 H 4 )NbH] 2 ; H 2 photoelimination was proposed as the primary photoprocess. 157…”

Section: Group 4 Metalsmentioning

confidence: 99%

Photochemistry of Transition Metal Hydrides

2016

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“…41 The molecular structures of [TaMe 3 Cl 2 ] and [Ta(PMe 3 ) 2 Me 3 Cl 2 ] were determined. 42 45 NMR spectroscopy, X-ray crystallography and DFT studies have shown that the diazabuta-1,3-diene rings are inequivalent in [CpM( i PrDAB) 2 ] (M = Nb, Ta; i PrDAB = bis-isopropyl-1,4-diazabuta-1,3-diene). 46 The reaction between the TaXCl 4 (X = Cl, Z 5 -C 5 H 5 , Z 5 -C 5 H 4 (SiMe 3 ), Z 5 -C 5 Me 5 ) and [Li{C 6 H 4 (2-CH 2 NMe 2 )}] gives the cyclometallated aryl tetra-or trichlorido cyclopentadienyl tantalum complexes [TaXCl 3 {C 6 H 4 (2-CH 2 NMe 2 )-k 2 C,N}] (X = Cl, Z 5 -C 5 H 5 , Z 5 -C 5 H 4 (SiMe 3 ), Z 5 -C 5 Me 5 ).…”

Section: Niobium and Tantalummentioning

confidence: 99%

Vanadium, niobium and tantalum

Fulton

2012

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This Chapter reviews the literature concerning the group 5 elements that has been reported during 2011. The syntheses of new coordination and organometallic compounds are summarised, in addition to a review of their applications in the areas of catalysis and biological/medicinal chemistry. HighlightsUtilising vanadium nitrogenase in the reduction of carbon monoxide to hydrocarbons took a step forward as methods to expand the carbon chain to four were successful. 1 In addition, the source of hydrogen in this reduction reaction was found to be simple protons.

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Nb Complexes

Kurogi

Mindiola

2021

Comprehensive Coordination Chemistry III

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Synthesis and reactivity of [2]disilaniobocenophanes

Cited by 4 publications

References 53 publications

Photochemistry of Transition Metal Hydrides

Photochemistry of Transition Metal Hydrides

Vanadium, niobium and tantalum

Nb Complexes

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