Chemical bond activation on surface sites generated photochemically from Rh{sup I}(CO){sub 2} species
- Univ. of Pittsburgh, PA (United States)
The activation of chemical bonds in molecules on photochemically produced Rh{sup I} sites is reviewed in this article. The focus is primarily on the Rh{sup I}(CO) species generated during the ultraviolet photolysis of the well-known Rh{sup I}(CO){sub 2} species supported on an aluminum oxide surface (designated Rh{sup I}(CO){sub 2}/Al{sub 2}O{sub 3}). The Rh{sup I}(CO){sub 2} surface species is the heterogeneous analogue of the homogeneous phase CpRh(CO){sub 2} and Cp{sup *}Rh(CO){sub 2} (Cp{sup *} = {eta}{sup 5}-C{sub 5}(CH{sub 3}){sub 5}; Cp = {eta}{sup 5}-C{sub 5}H{sub 5}) known for its ability to activate the C-H bond in alkanes during ultraviolet irradiation. Here the authors review some of the key studies that have led to the molecular understanding of the activation of the Rh{sup I}(CO){sub 2}/Al{sub 2}O{sub 3} species by photochemical methods. Relevant examples of the homogeneous-phase bond activation studies utilizing a rhodium center will be discussed as well as theoretical studies that have provided valuable information regarding the active nature of the photoproduced Rh site. This will be followed by a review of recent photochemical studies of surface-bound Rh{sup I}(CO){sub 2}. The coordinatively unsaturated Rh{sup I}(CO) species produced photochemically can activate the C-H bond in C{sub 6}H{sub 12} and CH{sub 4}, the H-H bond in H{sub 2}, the O{double_bond}O bond in O{sub 2}, and the C{double_bond}O bond in CO{sub 2}.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- OSTI ID:
- 352683
- Journal Information:
- Langmuir, Journal Name: Langmuir Journal Issue: 10 Vol. 15; ISSN LANGD5; ISSN 0743-7463
- Country of Publication:
- United States
- Language:
- English
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