Monothiocarbamate complexes of rhodium(I)

doi:10.1016/S0020-1693(00)94877-1

Inorganica Chimica Acta

Volume 7, 1973, Pages 528-530

https://doi.org/10.1016/S0020-1693(00)94877-1 Get rights and content

Abstract

The preparation of some dicarbonyl(N-substituted-monothiocarbamato)rhodium(I) complexes is described. The red crystalline compounds are dimeric in chloroform solution and their infrared spectra in the terminal carbonyl region consist of three bands. These observations suggest that the structure of the compounds is similar to that of [Rh(co)₂Cl]₂ with the sulphur atoms of the monothiocarbamate ligands bridging the two rhodium(I) ions in the dimer. The reaction of the dimeric species with excess ligand and triphenyl-phosphine is also described. The monothiocarbamate acts as a monodentate ligand bonded through the sulphur atom only, in the products formed in these reactions.

References (18)

R.J. Magee et al.
Inorg. Chim. Acta
(1971)
E.M. Krankovits et al.
Inorg. Nucl. Chem. Letters
(1971)
J. Willemse
Inorg. Nucl. Chem. Letters
(1972)
B.J. McCormick et al.
Inorg. Nucl. Chem. Letters
(1972)
E.M. Krankovits et al.
Aust. J. Chem.
(1973)
B.J. McCormick et al.
Inorg. Chem.
(1972)
E.M. Krankovits et al.
Aust. J. Chem.
(1973)
C.G. Pierpont et al.
Chem. Commun.
(1972)
P. Jennische et al.
Acta Chem. Scand.
(1971)

There are more references available in the full text version of this article.

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Monothiocarbamate complexes of rhodium(I)

Abstract

Inorg. Chim. Acta

Inorg. Nucl. Chem. Letters

Inorg. Nucl. Chem. Letters

Inorg. Nucl. Chem. Letters

Aust. J. Chem.

Inorg. Chem.

Aust. J. Chem.

Chem. Commun.

Acta Chem. Scand.