Synthesis, crystal structure, and thermal behavior of a diiron toluenethiolate complex with triphenylphosphine coligand
- PDF / 1,520,411 Bytes
- 7 Pages / 595.276 x 790.866 pts Page_size
- 25 Downloads / 252 Views
Synthesis, crystal structure, and thermal behavior of a diiron toluenethiolate complex with triphenylphosphine coligand Jacob A. Martinez2 · Nikolay N. Gerasimchuk3 · Charles A. Mebi1 Received: 22 April 2020 / Accepted: 10 June 2020 © Springer Nature Switzerland AG 2020
Abstract A bis(p-toluenethiolato) dinuclear-carbonyl complex with triphenylphosphine coligand, [μ-(SC6H4CH3-p)2Fe2(CO)5(PPh3)], has been synthesized from [μ-(SC6H4CH3-p))2Fe2(CO)6] via facile CO substitution by P Ph3 in 33% yield. The structure of [μ-(SC6H4CH3-p)2Fe2(CO)5(PPh3)] has been determined by X-ray crystallography and spectroscopic measurements. In the solid state, the compound adopts a butterfly conformation with anti-orientation of the p-tolyl groups and apical position of triphenylphosphine. Thermogravimetric studies reveal that [μ-(SC6H4CH3-p)2Fe2(CO)5(PPh3)] undergoes sequential decomposition eliminating all of the CO ligands at ca 197 °C, followed by cleavage of the tolyl and PPh3 groups below ca 258 °C.
Introduction Hydrogenases are metalloenzymes that catalyze the reversibly production and oxidation of molecular hydrogen. One type of hydrogenase enzyme is [Fe–Fe]-hydrogenase, reported to be the most efficient catalyst for hydrogen production. The structure of the active site of [Fe–Fe]-hydrogenase (Fig. 1a) features a moiety bound to bridging dithiolate with carbonyl and cyano ligands. The [Fe2S2] unit is connected to [Fe4S4]-cubane clusters acting as electron transport chain [1–4]. There is considerable interest in the study of iron-carbonyl complexes that mimic the structure and/or function of the [Fe2S2] component of [Fe–Fe]-hydrogenase [5–9]. Our research team has been exploring such compounds using aromatic thiolate ligands in systems with all carbonyl ligands or monosubstituted phosphine derivatives Electronic supplementary material The online version of this article (https://doi.org/10.1007/s11243-020-00409-5) contains supplementary material, which is available to authorized users. * Charles A. Mebi [email protected] 1
Department of Physical Sciences, College of Natural and Health Sciences, Arkansas Tech University, 1701 N. Boulder Ave, Russellville, AR 72801, USA
2
Department of Biological Sciences, College of Natural and Health Sciences, Arkansas Tech University, 1701 N. Boulder Ave, Russellville, AR 72801, USA
3
Department of Chemistry, Missouri State University, 901 S. National Ave, Springfield, MO 65897, USA
(Fig. 1b) [10–14]. The aromatic thiolate ligands, through electron delocalization, influence the stability and electrochemical properties of the diiron center [11, 15, 16]. Earlier, we reported the synthesis and characterization of the complex, [μ-(SC6H4CH3-p))2Fe2(CO)6], compound 1 (Fig. 2) [14]. Compound 1 was shown to be an effective catalyst for the reduction of proton to molecular hydrogen with an over potential of 0.76 V. Crystal structure of compound 1 has been determined and the structural parameters reported [17]. In this study, the synthesis, molecular structure, and thermal proper
Data Loading...
