Issue 30, 2017
From the journal:

Dalton Transactions

A mononuclear iron carbonyl complex [Fe(μ-bdt)(CO)2(PTA)2] with bulky phosphine ligands: a model for the [FeFe] hydrogenase enzyme active site with an inverted redox potential†

M. Natarajan,a   H. Faujdar,a   S. M. Mobin, ORCID logo ‡b   M. Stein ORCID logo *c  and  S. Kaur-Ghumaan ORCID logo *a  

* Corresponding authors

a Department of Chemistry, University of Delhi, Delhi 110007, India
E-mail: skaur@chemistry.du.ac.in

b National Single Crystal X-ray Diffraction Facility, IIT Bombay, Powai, Mumbai 400076, India

c Max-Planck-Institute for Dynamics of Complex Technical Systems, Molecular Simulations and Design Group, Sandtorstrasse 1, 39106 Magdeburg, Germany
E-mail: matthias.stein@mpi-magdeburg.mpg.de
Fax: +49-391-6110403

Abstract

A mononuclear hexa-coordinated iron carbonyl complex [Fe(μ-bdt)(CO)2(PTA)2] 1 (bdt = 1,2-benzenedithiolate; PTA = 1,3,5-triaza-7-phosphaadamantane) with two bulky phosphine ligands in the trans position was synthesized and characterized by X-ray structural analysis coulometry data, FTIR, electrochemistry and electronic structure calculations. The complex undergoes a facilitated two-electron reduction 1/12− and shows an inverted one-electron reduction for 1/1− at higher potentials. Electrochemical investigations of 1 are compared to the closely related [Fe(bdt)(CO)2(PMe3)2] compound. A mechanistic suggestion for the hydrogen evolution reaction upon proton reduction from acid media is derived. The stability of 1 in both weak and strong acids is monitored by cyclic voltammetry.

Graphical abstract: A mononuclear iron carbonyl complex [Fe(μ-bdt)(CO)2(PTA)2] with bulky phosphine ligands: a model for the [FeFe] hydrogenase enzyme active site with an inverted redox potential

About
Cited by
Related
Download options Please wait...

Supplementary files

Article information

DOI
https://doi.org/10.1039/C7DT01994G
Article type
Paper
Submitted
01 Jun 2017
Accepted
04 Jul 2017
First published
10 Jul 2017
This article is Open Access
Creative Commons BY license

Dalton Trans., 2017,46, 10050-10056

Permissions

Request permissions

A mononuclear iron carbonyl complex [Fe(μ-bdt)(CO)2(PTA)2] with bulky phosphine ligands: a model for the [FeFe] hydrogenase enzyme active site with an inverted redox potential

M. Natarajan, H. Faujdar, S. M. Mobin, M. Stein and S. Kaur-Ghumaan, Dalton Trans., 2017, 46, 10050 DOI: 10.1039/C7DT01994G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements