Redox behaviour of mixed-ligand five-coordinate cobalt(I) complexes with isocyanides and phosphines

doi:10.1016/S0020-1693(00)91961-3

Inorganica Chimica Acta

Volume 38, 1980, Pages 207-212

https://doi.org/10.1016/S0020-1693(00)91961-3 Get rights and content

Abstract

The oxidation mechanism of a series of mixed-ligand five-coordinate cobalt(I) complexes of the type [Co(CNR)₃L₂]⁺ (R = C₆H₅, 4-CH₃C₆H₄, 4-CH₃OC₆H₄, 4-NO₂C₆H₄, and 2,6-(CH₃)₂C₆H₃; L = P(OCH₃)₃ and P(C₆H₅)(OC₂H₅)₂) on mercury and platinum electrodes in dichloromethane is described. The primary reversible electron transfer between electrode and depolarizer is followed by a fast chemical reaction which brings about a change in configuration (and a dimerization). Correlations between redox properties of the species and their structural features are discussed.

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Cited by (9)

Metal Isocyanide Complexes
1983, Advances in Organometallic Chemistry
This chapter discusses metal–isocyanide chemistry. In the interim, reviews have appeared on specific aspects of isocyanide chemistry. The generally accepted valence bond and molecular orbital (MO) approach to the bonding of metal isocyanides has been well described in Treichel's review, and has been used to rationalize variations in infrared (IR) stretching frequencies between bonded and nonbonded isocyanides and the better π-acceptor qualities of aryl versus alkyl isocyanide groups. A number of new synthetic routes to isocyanide complexes of chromium, molybdenum, and tungsten have been investigated. A number of attempts have been made over the years to develop reproducible synthetic routes to six- and seven-coordinate isocyanide complexes of molybdenum and tungsten. A number of routes have been employed for the synthesis of metal–isocyanide complexes by generating the isocyanide ligand on the metal atom. A number of monomeric complexes have been prepared, which may be considered as substitution products of the [Co(CNR)₅]⁺ and [M(CNR)₄]⁺ cations. Electrochemical investigations have been reported on a range of homoleptic and mixed carbonyl–isocyanide complexes, in attempts to rationalize substituent effects on the isocyanide with the electronic structure of the metal. Insertion reactions of isonitriles into metal–alkyl or metal–aryl bonds are now well established, occurring with metal–alkyl or –aryl groups from group IVA to IB and, recently, with uranium and thorium carbon bonds.
Cobalt, rhodium and iridium annual survey covering the year 1980
1982, Journal of Organometallic Chemistry
Electrochemical studies on mixed-ligand iron(II) complexes containing isocyanides and phosphines
1982, Journal of Organometallic Chemistry
Voltammetry at a stationary platinum electrode and polarography were carried out in dichloromethane (0.1 mol dm⁻³ tetrabutylammonium perchlorate as supporting electrolyte) for complexes of the type [FeX(CNR)₂L₃][ClO₄] [X = Cl, Br or I; L = PPh(OEt)₂; R = phenyl, 4-methylphenyl, 4-methoxyphenyl, 2-methylphenyl or 2,6-dimethylphenyl] and for [Fe(CNR)₃L₃][ClO₄]₂ [L = PPh(OEt)₂; R = cyclohexyl]. A mechanism of the redox process for both oxidation and reduction is postulated. A simple redox change without any complication from chemical reaction occurs in the case of oxidation at a platinum elec $t$ rode, whereas the reduction is complicated by a subsequent chemical reaction.
Cobalt
1982, Coordination Chemistry Reviews
Redox behaviour of rhodium(I) and iridium(I) with schiff bases derived from pyridine-2-aldehyde and some primary amines including the optically active α-phenylethylamine
1981, Journal of Organometallic Chemistry
The polarographic and voltammetric behaviour of complexes of the type [M(Chel)cod]PF₆(M=Rh, Ir; Chel=pyridinalmethyliminde, pyridinal-isopropylimine, pyridinal-α-phenylethylimine; cod=cyclooctadiene) have been studied in acetonitrile and dichloroethane with 0.1 M tetrabutylammonium perchlorate as supporting electrolyte. The reduction proceeds in two reversible one-electron steps, followed by one or two irreversible waves, complicated by adsorption phenomena and chemical side reactions. The electrooxidation shows only a single one-electron step, associated to catalytic phenomena at the electrode. The electrochemical data suggest that the pyridinalphenylethylimine derivative must be the most active reduction catalyst among the above complexes.
Tris(tert-butyl isocyanide)bis-[tris-(4-methoxy-phen-yl)phosphine]cobalt(I) perchlorate dichloro-methane disolvate and tris-(tert-butyl isocyanide)bis-[tris-(4-methoxy-phenyl)phosphine]cobalt(II) bis-(perchlorate) dichloro-methane disolvate: Modification of a trigonal-bipyramidal structure with change of metal oxidation state
2010, Acta Crystallographica Section C: Crystal Structure Communications

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Redox behaviour of mixed-ligand five-coordinate cobalt(I) complexes with isocyanides and phosphines

Abstract

Coord. Chem. Revs.

J. Organometal. Chem.

Inorg. Nucl. Chem. Letters

Electrochim. Acta

Inorg. Chem.

Chem. Listy

J. Chem. Soc. Dalton

J. Chem. Soc. Dalton

Inorg. Chem.

Inorg. Chem.

Inorg. Chem.

Chem. Listy

Anal. Chem.