Use of the electron-reservoir [Fe{sup I}Cp(arene)] sandwiches as efficient and selective electrocatalysts: Syntheses of homo- and heterodinuclear zwitterionic transition-metal fulvalene complexes
- Univ. of California, Berkeley, CA (United States)
- Universite Bordeaux, Talence (France)
The electron-reservoir complexes [Fe{sup I}Cp(C{sub 6}H{sub 6})], [Fe{sup I}Cp(C{sub 6}Me{sub 6})], and [Fe{sup I}Cp{sup *}(C{sub 6}Me{sub 6})] (Cp = {eta}{sup 5}-C{sub 5}H{sub 5}; Cp{sup *} = {eta}{sup 5}-C{sub 5}Me{sub 5}) have been used as initiators in THF for the electron-transfer-chain-catalyzed (electrocatalyzed) synthesis of the homobimetallic zwitterions [(CO){sub 3}M{sup -}FvM{sup +}(CO){sub 2}(PR{sub 3}){sub 2}] (M = Mo, W; Fv = {mu}{sub 2}-{eta}{sup 10}-fulvalene; R = Me, OMe) from [M{sub 2}Fv-(CO){sub 6}] and PR{sub 3} and of the heterobimetallic zwitterions [(CO){sub 3}M{sup I}FvM{sup 2}(CO)(PR{sub 3}){sub 2}] (M{sup 1} = Mo, W; M{sup 2} = Fe, Ru) from [M{sup 1}M{sup 2}Fv(CO){sub 5}] and PR{sub 3}. Cyclic voltammetry (CV) experiments (DMF, 0.1 M n-Bu{sub 4}NBF{sub 4}, Pt, 0.400 V s{sup -1}) show that the CV`s of the homobimetallic starting materials are unchanged in the presence of PR{sub 3} (R = Me, OMe) whereas those of the heterobimetallic complexes in the presence of PMe{sub 3} show only the CV`s of the zwitterions. This indicates that the electrocatalytic process of the homobimetallic complexes is slow on the electrochemical time scale whereas that of the heterobimetallic complexes with PMe{sub 3} is fast on the same time scale. 84 refs., 2 figs., 3 tabs.
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 249682
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 9 Vol. 15; ISSN 0276-7333; ISSN ORGND7
- Country of Publication:
- United States
- Language:
- English
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