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Diimine-Acetylide Compounds of Ruthenium: The Structural and Spectroscopic Effects of Oxidation

Adams, Christopher J. and Pope, Simon J. A. 2004. Diimine-Acetylide Compounds of Ruthenium: The Structural and Spectroscopic Effects of Oxidation. Inorganic Chemistry 43 (11) , pp. 3492-3499. 10.1021/ic035181v

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Abstract

The reaction of Ru(Me2bipy)(PPh3)2Cl2 1 with terminal alkynes HCCR in the presence of TlPF6 leads to the formation of the vinylidene compounds [Ru(Me2bipy)(PPh3)2Cl(CCHR)][PF6] (2) (2a, R = But; 2b, R = p-C6H4−Me; 2c, R = Ph). These compounds decompose in oxygenated solution to form the carbonyl compound [Ru(Me2bipy)(PPh3)2Cl(CO)][PF6] (3), and may be deprotonated by K2CO3 to give the ruthenium(II) terminal acetylide compounds Ru(Me2bipy)(PPh3)2Cl(CC−R) (4) (4a, R = But; 4b, R = p-C6H4−Me; 4c, R = Ph). Cyclic voltammetry shows that 2a−c may also be reductively dehydrogenated to form 4a−c. 4a−c are readily oxidized to their ruthenium(III) analogues [4a]+−[4c]+, and the changes seen in their UV/visible spectra upon performing this oxidation are analyzed. These show that whereas the UV/visible spectra of 4a−c show MLCT bands from the ruthenium atom to the bipyridyl ligand, those of [4a]+−[4c]+ contain LMCT bands originating on the acetylide ligands. This is in agreement with the IR and ESR spectra of [4a]+−[4c]+. The X-ray crystal structures of the redox pair 4a and [4a][PF6] have been determined, allowing the bonding within the metal−acetylide unit to be analyzed, and an attempt is made to determine Lever electrochemical parameters (EL) for the vinylidene and acetylide ligands seen herein. Room temperature luminescence measurements on 4a−c show that the compounds are not strongly emissive.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 0020-1669
Last Modified: 04 Jun 2017 04:37
URI: http://orca.cf.ac.uk/id/eprint/41640

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