Jump to main content
Jump to site search

Issue 23, 2003
Previous Article Next Article

The reaction of [{Co(η5-C5H5)}2{Fe(CO)2(PPh3)}(μ3-S)(μ3-CS)] and related complexes with carbon disulfide. Synthesis, structure and reactivity of [{Co(η5-C5H5)}2{Fe(CO)(L)}(μ3-S)(μ3-C2S3)] derivatives (L = PR3 and CNR)

Author affiliations

Abstract

[{Co(η5-C5H5)}2{Fe(CO)(L)2}(μ3-S)(μ3-CS)] complexes 1 where (L)2 = (a) (CO)(PPh3), (b) (CO){P(OPh)3}, (c) (CO)(PBun3), (d) (CNMe)2 and (e) (CNMes)2 (Mes = 2,4,6-Me3C6H2), but not (CO)(CNMes), react with CS2 under reflux to give [{Co(η5-C5H5)}2{Fe(L)2}(μ3-S)(μ3-C2S3)], 2, in which a CS2 molecule has been incorporated into a FeSC(S*)SC heterocycle with a trithiocarbonate moiety bridging the Fe–C cluster edge. Clusters 2 react with incoming ligands either by simple ligand substitution, or by displacement of CS2 to form clusters of type 1. The exocyclic sulfur atom S* is nucleophilic and with electrophiles E forms [{Co(η5-C5H5)}2{Fe(L)2}(μ3-S)(μ3-C2S3E] adducts which contain S*→E bonds where E = Me+ [3]+, Et+ [4]+, HgCl2 [5], and I4 (or I+) [6]. The clusters 2a–c and the [3]+ and [4]+ derived from them are chiral as indicated by their NMR spectra, and do not racemize on the NMR timescale. The structures of 2a·2C6H6 and [3a]I·C6H6·CHCl3 are reported. Cluster 2a contains a very short Fe–Cμ bond as compared with 1a, and it is suggested that in many respects the FeSC(S)SCμ ring is best regarded as a metallo-1,3-dithiole-2-thione (or metallovinyl trithiocarbonate) with a Fe–Cμ double bond which, on alkylation at the exocyclic S*, adopts a more delocalised electronic structure with a longer Fe–Cμ bond. Spectroscopic and electrochemical data for the new compounds are discussed.

Graphical abstract: The reaction of [{Co(η5-C5H5)}2{Fe(CO)2(PPh3)}(μ3-S)(μ3-CS)] and related complexes with carbon disulfide. Synthesis, structure and reactivity of [{Co(η5-C5H5)}2{Fe(CO)(L)}(μ3-S)(μ3-C2S3)] derivatives (L = PR3 and CNR)

Back to tab navigation

Supplementary files

Additions and corrections

Article information


Submitted
21 Jul 2003
Accepted
18 Sep 2003
First published
29 Sep 2003

Dalton Trans., 2003, 4472-4481
Article type
Paper

The reaction of [{Co(η5-C5H5)}2{Fe(CO)2(PPh3)}(μ3-S)(μ3-CS)] and related complexes with carbon disulfide. Synthesis, structure and reactivity of [{Co(η5-C5H5)}2{Fe(CO)(L)}(μ3-S)(μ3-C2S3)] derivatives (L = PR3 and CNR)

A. R. Manning, C. J. McAdam, A. J. Palmer, B. H. Robinson and J. Simpson, Dalton Trans., 2003, 4472
DOI: 10.1039/B308320A

Social activity

Search articles by author

Spotlight

Advertisements