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          Institute: MPI für bioanorganische Chemie     Collection: MPI für bioanorganische Chemie     Display Documents



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ID: 708901.0, MPI für bioanorganische Chemie / MPI für bioanorganische Chemie
Synthesis, Reactivity, and Electronic Structure of a Bioinspired Heterobimetallic [Ni( μ-S2)Fe] Complex with Disulfur Monoradical character
Authors:Rudolph, Robert; Blom, Burgert; Yao, Shenglai; Meier, Florian; Bill, Eckhard; van Gastel, Maurice; Lindenmaier, Nils; Kaupp, Martin; Driess, Matthias
Date of Publication (YYYY-MM-DD):2014
Title of Journal:Organometallics
Journal Abbrev.:Organometallics
Volume:33
Issue / Number:12
Start Page:3154
End Page:3162
Review Status:Internal review
Audience:Experts Only
Abstract / Description:The first synthesis of a monoradical Ni(mu-S-2)Fe core in the [(Nacnac)Ni(mu-S-2)Fe(dmpe)(2)] complex 3 could be accomplished in good yields by PMe3 elimination from the zerovalent iron complex [(dmpe)(2)(PMe3)Fe] (2; dmpe = 1,2-bis(dimethylphosphine)ethane) upon reaction with the supersulfido nickel(II) complex [(Nacnac)Ni(S-2)] (1; Nacnac = CH{(CMe)(2,6-(Pr2C6H3N)-Pr-i)}(2)). Complex 3 bears Ni(II) and Fe(II) centers, both of which are in a low-spin state. A single electron is located in the HOMO and is somewhat delocalized over the Ni(mu-S-2)Fe core, so that the bridging disulfur subunit exhibits some "subsulfide" S-2(3-) character. Compound 3 represents a bioinspired example of a monoradical with a Ni(mu-S-2)Fe structural motif, reminiscent of the Ni(mu-S-2)Fe core structure of the active site in [NiFe] hydrogenases. Its oxidation with [Fe(eta(5)-C5H5)(2)][B(C6H3(CF3)(2))(4)] affords the product [(Nacnac)Ni(mu-S)(2)Fe(dmpe)(2)][B(C6H3(CF3)(2))(4)] (4), and complex 3 can alternatively be prepared via a reductive route upon reaction of [Co(eta(5)-C5Me5)(2)][(Nacnac)NiS2] (6) with the Fe(0) precursor 2. All synthesized complexes were fully characterized, including in some cases single-crystal X-ray diffraction analysis, magnetometry, EPR, NMR, and Fe-57 Mossbauer spectroscopy. DFT calculations were used to compute the spectroscopic parameters and to establish the electronic structure of 3 and its oxidized and reduced forms and related complexes.
External Publication Status:published
Document Type:Article
Communicated by:N. N.
Affiliations:MPI für bioanorganische Chemie
External Affiliations:[Rudolph,R.; Blom,B.; Yao,S.L.; Meier,F.; Lindenmaier,N.; Kaupp,M.; Driess,M.;]Tech.Univ.Berlin, Dept.Chem., D-10623 Berlin, Germany.
Identifiers:ISI:000337936800023 [ID No:1]
ISSN:0276-7333 [ID No:2]
DOI:10.1021/om500381t [ID No:3]
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