Journal
DALTON TRANSACTIONS
Volume -, Issue 6, Pages 925-931Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/b814298j
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Funding
- EPSRC
- University of Nottingham
- CVCP ORS Awards Scheme
- Royal Society Wolfson Merit Award
- Royal Society Leverhulme Trust Senior Research Fellowship
- Engineering and Physical Sciences Research Council [EP/C528964/1] Funding Source: researchfish
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The synthesis and characterisation of the trinuclear Ni-Fe complex [Ni(L-2) SFe2(CO)(6)] (1) formed from the reaction of [Ni(L-1)] with Fe-3(CO)(12) is described. The single-crystal X-ray structure of 1 shows Ni(II) bound to three thioether R-2-S donors and bridged by a sulfide (S2-) group to two Fe(CO)(3) units. 1 undergoes a reversible one-electron reduction process at E-1/2 = -1.62 V vs. Fc(+)/Fc to generate 1(-), which has been characterised by UV-vis and IR spectroelectrochemistry and by EPR spectroscopy. DFT calculations on 1 and 1(-) reveal electronic structures that are delocalised across the NiFe2 core. The SOMO in 1(-) possesses Ni-Fe and Fe-Fe anti-bonding character and lies approximately in the plane defined by the equilateral triangle of Ni and Fe atoms. It possesses d-orbital contributions of 18.5, 15.0 and 19.8% for the Ni(1), Fe(1) and Fe(2) atoms, respectively. The Ni-S(sulfide) bond length in 1 [2.1654(7)angstrom] is identical to that for the bridging sulfide found in the oxidised inactive form of the [NiFe] hydrogenase from D. vulgaris (2.16 angstrom). Thus, 1 provides a useful comparison for biological [NiFe] centres bridged by sulfide donors.
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