Redox chemistry of ruthenium porphyrins: evidence for internal electron transfer and the characterization of [RuIII(OEP+˙)] species

1981 ◽  
pp. 982-983 ◽  
Author(s):  
Mark Barley ◽  
James Y. Becker ◽  
George Domazetis ◽  
David Dolphin ◽  
Brian R. James
Keyword(s):  
Electron Transfer ◽  
Redox Chemistry ◽  
Internal Electron

Synthesis and redox chemistry of octaethylporphyrin complexes of ruthenium(II) and ruthenium(III)

1983 ◽  
Vol 61 (10) ◽  
pp. 2389-2396 ◽  
Author(s):  
Mark Barley ◽  
James Y. Becker ◽  
George Domazetis ◽  
David Dolphin ◽  
Brian R. James
Keyword(s):  
Electron Transfer ◽  
Electrochemical Oxidation ◽  
Ground State ◽  
Ligand Exchange ◽  
Cation Radical ◽  
Electron Transfer Process ◽  
Porphyrin Ligand ◽  
Tertiary Phosphines ◽  
Internal Electron

The syntheses and characterization of some new octaethylporphyrin complexes of ruthenium(II) and ruthenium(III) are described; the complexes are Ru(OEP)(P″Bu3)2, Ru(OEP)(CO)L (L = PPh3, P″Bu3), [Ru(OEP)(P″Bu3)2]Br, and Ru(OEP)(P″Bu3)Br, where OEP is the dianion of octaethylporphyrin. The Ru(OEP)(CO)EtOH complex, 1, which reversibly loses the ethanol ligand in CH2Cl2 solution, undergoes a one-equivalent oxidation at the porphyrin ligand to generate the cation-radical [Ru(OEP)•+(CO)]+; a purple species of 2A2u ground state, produced electrochemically in perchlorate media, can coordinate bromide to generate a green 2A1u ground state species that also results from oxidation of 1 using bromine. Coordination of pyridine to [Ru(OEP)•+(CO)]+ yields the Ru(OEP)•+(CO)py species that can also be formed by electrochemical oxidation of Ru(OEP)(CO)py. Addition of tertiary phosphines (PR3) to the cation-radical carbonyl species can lead to formation of [Ru(OEP)(PR3)2]+, via an internal electron transfer process from Ru(II) to the OEP•+ that appears to be triggered by loss of the CO ligand. A reversible one-electron electrochemical oxidation of Ru(OEP)(P″Bu3)2 at 0.03 V (vs. Ag/AgCl) in CH2Cl2 also gives the ruthenium(III) biphosphine cation, while a further one-electron oxidation at 1.2 V generates [Ru(OEP)•+(P″Bu3)2]2+, a ruthenium(III) π-cation radical characterized by esr. The [Ru(OEP)(P″Bu3)2]Br complex decomposes in the solid state to a mixture of Ru(OEP)(P″Bu3)Br, formed together with free phosphine via an intramolecular ligand exchange, and Ru(OEP)(P″Bu3)2, formed by reduction of the initial ionic ruthenium(III) cation with the phosphine that appears as [P″Bu3Br]Br.

Synthesis and Characterization of C70-Corrole—A New Electron Transfer Dyad

2014 ◽  
Vol 14 (7) ◽  
pp. 5370-5374 ◽  
Author(s):  
Youde Wang ◽  
Zhenzhen Wang ◽  
Xihong Guo ◽  
Rongli Cui ◽  
Xingfa Gao ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Synthesis And Characterization

Redox Chemistry of (1,4,7-Tris(4-tert-butyl-2-mercaptobenzyl)-1,4,7- triazacyclononane)ruthenium(III), [RuIIIL]:  Synthesis and Characterization of [RuII2(L−L)](BPh4)4·10CH3CN and [LRuRuRuL](PF6)2·H2O

1999 ◽  
Vol 38 (22) ◽  
pp. 5131-5138 ◽  
Author(s):  
Belén Albela ◽  
Eberhard Bothe ◽  
Oliver Brosch ◽  
Katsura Mochizuki ◽  
Thomas Weyhermüller ◽  
...  
Keyword(s):  
Redox Chemistry ◽  
Synthesis And Characterization ◽  
Tert Butyl
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