Mixed-metal Cluster Synthesis: [Re(CO)₃(μ-S₂NC₇H₄)]₂ as a Precursor for tri- and tetranuclear 2-mercaptobenzothiolato Capped Clusters

Authors

Shishir Ghosh, Jahangirnagar UniversityFollow
Kamrun N. Khanam, Jahangirnagar UniversityFollow
Md. Kamal Hossain, Jahangirnagar University
G. M. Golzar Hossain, University of Dhaka
Daniel T. Haworth, Marquette UniversityFollow
Sergey V. Lindeman, Marquette UniversityFollow
Graeme Hogarth, University College London
Shariff E. Kabir, Jahangirnagar University

Document Type

Article

Language

eng

Format of Original

9 p.

Publication Date

4-15-2010

Publisher

Elsevier

Source Publication

Journal of Organometallic Chemistry

Source ISSN

0022-328X

Abstract

The readily prepared [Re₂(CO)₆(μ-S₂NC₇H₄)₂] (1) reacts with Group 8 trimetallic carbonyl clusters to yield new mixed-metal tri- and tetranuclear clusters. With [Os₃(CO)₁₀(NCMe)₂] at 80 °C the tetranuclear mixed-metal cluster [Os₃Re(CO)₁₃(μ₃-C₇H₄NS₂)] (2) is the only isolated product. With Ru₃(CO)₁₂ products are dependent upon the reaction temperature. At 80 °C, a mixture of tetranuclear mixed-metal [Ru₃Re(CO)₁₃(μ₃-C₇H₄NS₂)] (5) and the triruthenium complex [Ru₃(CO)₉(μ-H)(μ₃-C₇H₄NS₂)] (4) results, while at 110 °C a second tetranuclear mixed-metal cluster, [Re₂Ru₂(CO)₁₂(μ₄-S)(μ-C₇H₄NS)(μ-C₇H₄NS₂)] (3), resulting from carbon–sulfur bond scission, is the major product. Reaction of 1 With Fe₃(CO)₁₂ at 80 °C furnishes the trinuclear mixed-metal cluster [Fe₂Re(CO)₈(μ-CO)₂(μ₃-C₇H₄NS₂)] (6). The reactivity of 6 has been probed with the aim of identifying any metal-based selectivity for carbonyl substitution. Addition of PPh₃ in presence of Me₃NO at 25 °C gives both the mono- and bis(phosphine)-substituted derivatives [Os₃Re(CO)₁₂(PPh₃)(μ₃-C₇H₄NS₂)] (7) and [Os₃Re(CO)₁₁(PPh₃)₂(μ₃-C₇H₄NS₂)] (8). In 7 the PPh₃ ligand occupies an axial site on wingtip osmium, while in 8 one PPh₃ ligand is equatorially coordinated to wingtip osmium and the other is bonded to a hinge osmium. New complexes have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction studies.

Comments

Accepted version. Journal of Organometallic Chemistry, Vol. 695, No. 8 (April 15, 2010): 1146-1154. DOI. © 2010 Elsevier. Used with permission.

Recommended Citation

Ghosh, Shishir; Khanam, Kamrun N.; Hossain, Md. Kamal; Hossain, G. M. Golzar; Haworth, Daniel T.; Lindeman, Sergey V.; Hogarth, Graeme; and Kabir, Shariff E., "Mixed-metal Cluster Synthesis: [Re(CO)₃(μ-S₂NC₇H₄)]₂ as a Precursor for tri- and tetranuclear 2-mercaptobenzothiolato Capped Clusters" (2010). Chemistry Faculty Research and Publications. 548.
https://epublications.marquette.edu/chem_fac/548