Reactions of hydrogen or deuterium molecule with a rhodium(II) metalloradical: kinetic evidence for a four-centered transition state

Wayland, Bradford B.; Ba, Sujuan; Sherry, Alan E.

doi:10.1021/ic00027a031

Cited by 77 publications

(65 citation statements)

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“…59(a). Similar kinetic studies suggest that toluene and methane CÀ ÀH bond cleavage reactions (and also HÀ ÀH bond reactions of H 2 ) proceed via related mechanisms (166,168,169).…”

Section: )] and [Rh III (Por)(h)]mentioning

confidence: 68%

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

Bruin

Hetterscheid

Koekkoek

et al. 2007

Progress in Inorganic Chemistry

121

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“…59(a). Similar kinetic studies suggest that toluene and methane CÀ ÀH bond cleavage reactions (and also HÀ ÀH bond reactions of H 2 ) proceed via related mechanisms (166,168,169).…”

Section: )] and [Rh III (Por)(h)]mentioning

confidence: 68%

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

Bruin

Hetterscheid

Koekkoek

et al. 2007

Progress in Inorganic Chemistry

121

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“…Finally, the reaction of two L tBu Fe species simultaneously with H 2 is possible (Scheme 6d). This reaction would be topologically similar to the homolytic cleavage of H 2 and alkanes by rhodium porphyrins, which has been demonstrated to be termolecular [35-37]. The monomeric hydride complexes would then dimerize to give [L tBu Fe(μ-H)] 2 .…”

Section: Resultsmentioning

confidence: 92%

New routes to low-coordinate iron hydride complexes: The binuclear oxidative addition of H2

Dugan

Holland

2009

Journal of Organometallic Chemistry

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The oxidative addition and reductive elimination reactions of H2 on unsaturated transition-metal complexes are crucial in utilizing this important molecule. Both biological and man-made iron catalysts use iron to perform H2 transformations, and highly unsaturated iron complexes in unusual geometries (tetrahedral and trigonal planar) are anticipated to give unusual or novel reactions. In this paper, two new synthetic routes to the low-coordinate iron hydride complex [LtBuFe(μ-H)]2 are reported. Et3SiH was used as the hydride source in one route by taking advantage of the silaphilicity of the fluoride ligand in three-coordinate LtBuFeF. The other synthetic method proceeded through the binuclear oxidative addition of H2 or D2 to a putative Fe(I) intermediate. Deuteration was verified through reduction of an alkyne and release of the deuterated alkene product. Mössbauer spectra of [LtBuFe(μ-H)]2 indicate that the samples are pure, and that the iron(II) centers are high-spin.

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“… a) Electronic structures of D 3 h and T‐shaped geometry in a d 9 system. b) C−H bond activation with the SOMO of a d 7 Rh porphyrin species ,…”

Section: Methodsmentioning

confidence: 99%

“…In addition to standard radical‐type reactions, reactions involving two metals can be a powerful way of enhancing the utility of the

d_{x^{2} - y^{2}}

based radical. For example, two Rh II ‐d 7 porphyrin complexes were previously shown to work together to activate methane, Scheme b ,. A similar strategy may be possible with T‐shaped d 9 species, but remains largely unexplored to date.…”

Section: Methodsmentioning

confidence: 99%

A T‐Shaped Nickel(I) Metalloradical Species

Yoo

Lee

2017

Angewandte Chemie

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A T‐shaped NiI complex was synthesized using a rigid acridane‐based pincer ligand to prepare a metalloradical center. Structural data displays a nickel ion is embedded in the plane of a PNP ligand. Having a sterically exposed half‐filled dx2-y2 orbital, this three‐coordinate NiI species reveals unique open‐shell reactivity including the homolytic cleavage of various σ‐bonds, such as H−H, N−N, and C−C.

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Reactions of hydrogen or deuterium molecule with a rhodium(II) metalloradical: kinetic evidence for a four-centered transition state

Cited by 77 publications

References 0 publications

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

The Organometallic Chemistry of Rh‐, Ir‐, Pd‐, and Pt‐Based Radicals: Higher Valent Species

New routes to low-coordinate iron hydride complexes: The binuclear oxidative addition of H2

A T‐Shaped Nickel(I) Metalloradical Species

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