Simple thiolate (L1 ) and amido (L2 ) SNS pincer ligands are prepared in one and two steps, respectively from commercial sources. Reaction of ligand HL1  with Fe(OTf)2 affords a trinuclear complex, {Fe[(�-SNS)2Fe]2}(OTf)2, that reacts with small donors such as P(OMe)3 to give binuclear, pseudo-octahedral {[FeL2(�-SNS)]2}(OTf)2. In contrast, [FeCl(PMe3)4]BPh4 and HL1  yield (PMe3H)Cl and mononuclear [Fe(SNS)(PMe3)3]BPh4 that converts slowly to trivalent [Fe(SNC)(PMe3)3]BF4 via facile C-S bond activation. Depending on order of addition, reaction of Fe[N(SiMe3)2]2 with HL1  affords binuclear {Fe[N(SiMe3)2](�-SNS)}2 or a novel 5-coordinate complex of the imine-coupled N2S2 ligand, 3 . Finally, reaction of Fe[N(SiMe3)2]2 with ligand HL2  gives 6-coordinate diamido complex Fe(SNS)2 which features two short Fe-S bonds to 5-membered ring chelating thioethers and two long Fe-S bonds to the 6-membered ring thioethers. The latter reaction also yields some of the 5-membered ring complex with only one 6-membered ring coordinated thioether. Preliminary reactivity of these complexes will also be described.

Hemilabile SNS pincer iron complexes: Facile C-S bond activation and imine coupling to redox-active N<sub>2</sub>S<sub>2</sub> ligand

248th National Meeting (2014)

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Hemilabile SNS pincer iron complexes: Facile C-S bond activation and imine coupling to redox-active N2S2 ligand

Hemilabile SNS pincer iron complexes: Facile C-S bond activation and imine coupling to redox-active N₂S₂ ligand