The synthesis and electronic structure of a novel [NiS4Fe2(CO)6] radical cluster: implications for the active site of the [NiFe] hydrogenases

Chemistry : a European Journal
Qiang WangMartin Schröder

Abstract

A novel [NiS4Fe2(CO)6]cluster (1: 'S(4)'=(CH(3)C(6)H(3)S(2))(2)(CH(2))(3)) has been synthesised, structurally characterised and has been shown to undergo a chemically reversible reduction process at -1.31 V versus Fc(+)/Fc to generate the EPR-active monoanion 1(-). Multifrequency Q-, X- and S-band EPR spectra of (61)Ni-enriched 1(-) show a well-resolved quartet hyperfine splitting in the low-field region due to the interaction with a single (61)Ni (I=3/2) nucleus. Simulations of the EPR spectra require the introduction of a single angle of non-coincidence between g(1) and A(1), and g(3) and A(3) to reproduce all of the features in the S- and X-band spectra. This behaviour provides a rare example of the detection and measurement of non-coincidence effects from frozen-solution EPR spectra without the need for single-crystal measurements, and in which the S-band experiment is sensitive to the non-coincidence. An analysis of the EPR spectra of 1(-) reveals a 24 % Ni contribution to the SOMO in 1(-), supporting a delocalisation of the spin-density across the NiFe(2) cluster. This observation is supported by IR spectroscopic results which show that the CO stretching frequencies, nu(CO), shift to lower frequency by about 70 cm(-1) whe...Continue Reading

Citations

Jul 21, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Li-Cheng SongXu-Yong Wang
Mar 4, 2006·Chemical Communications : Chem Comm·Alessandro PerraMartin Schröder
Jan 5, 2006·Chemical Communications : Chem Comm·Philip A StensonMartin Schröder
Oct 10, 2006·Physical Chemistry Chemical Physics : PCCP·Prabha JayapalNeil A Burton
Jun 22, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Li-Cheng SongHai-Bin Song
May 23, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Sandeep Kaur-Ghumaan, Matthias Stein
May 31, 2012·Physical Chemistry Chemical Physics : PCCP·Prabha Jayapal, Gopalan Rajaraman
Jan 29, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Alessandro PerraMartin Schröder
Nov 13, 2008·Inorganic Chemistry·Maurice van GastelWolfgang Lubitz
Apr 23, 2014·Inorganic Chemistry·Peter A SummersMartin Schröder

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