Issue 5, 1997

Thiobenzamidato and thiobenzoato complexes of ruthenium, osmium and iridium

Abstract

Thiobenzamide reacted with the complexes [MCl 2 (PPh 3 ) 3 ], [MH(X)(CO)(PPh 3 ) 3 ] (M = Ru or Os, X = H or Cl) and mer-[IrH 3 (PPh 3 ) 3 ] in boiling toluene to afford the products [M{S(NH)CPh} 2 (PPh 3 ) 2 ], [MX{S(NH)CPh}(CO)(PPh 3 ) 2 ] and [IrH 2 {S(NH)CPh}(PPh 3 ) 2 ] respectively. The crystal structure of [Os{S(NH)CPh} 2 (PPh 3 ) 2 ] confirms the expected bis(N,S-chelate) formulation and has established the presence of cis-phosphorus, cis-nitrogen and trans-sulfur donor atom pairs within a highly distorted octahedral co-ordination sphere. Thiobenzoic acid reacted with [MCl 2 (PPh 3 ) 3 ] and [MH(X)(CO)(PPh 3 ) 3 ] under similar conditions to yield [M{S(O)CPh} 2 (PPh 3 ) 2 ] and [M{S(O)CPh} 2 (CO)(PPh 3 ) 2 ] respectively. The reactions of thiobenzoic acid with mer-[IrH 3 (PPh 3 ) 3 ] under conditions of increasing severity give [IrH 2 {S(O)CPh}(PPh 3 ) 3 ], [IrH{S(O)CPh} 2 (PPh 3 ) 2 ] and [Ir{S(O)CPh} 3 (PPh 3 ) 2 ] the last two of which on carbonylation afford [IrH{S(O)CPh} 2 (CO)(PPh 3 ) 2 ] and [Ir{S(O)CPh} 3 (CO)(PPh 3 ) 2 ] respectively. The crystal structure of [IrH{S(O)CPh} 2 (PPh 3 ) 2 ] has established the presence of trans phosphorus and trans sulfur donor atom pairs, with the η 1 - and η 2 -thiobenzoate ligands sharing a meridional set of three co-ordination sites. However, the NMR spectra of this complex show two high-field 1 H triplets and two 31 P-{ 1 H} singlets. Possible explanations for this anomalous NMR behaviour, which is also found for the corresponding thioacetate, are advanced.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1997, 757-762

Thiobenzamidato and thiobenzoato complexes of ruthenium, osmium and iridium

S. D. Robinson, A. Sahajpal and D. A. Tocher, J. Chem. Soc., Dalton Trans., 1997, 757 DOI: 10.1039/A607011F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements