Divergent Interaction of (Iso)nitriles with a Linear Iron(I) Silylamide─A Combined Structural, Spectroscopic, and Computational Study.

Nitriles and isonitriles are important σ-donor ligands in coordination chemistry. Isonitriles also function in low-valent complexes as π-acceptor ligands similar to CO. Herein we present the unusual behavior of the highly reducing, high-spin iron(I) complex [Fe(hmds)2]- toward these compound classes. Rare examples of side-on coordination of nitriles to the metal center are observed. Insights gained by 57Fe Mössbauer spectroscopy as well as DFT and CASSCF calculations give an interplay between the resonance structures of not only an iron(I) π-complex and an iron(III) metallacycle but also point to the importance of an iron(II) nitrile radical anion. For an aromatic isonitrile end-on coordination is observed, which is best described as an iron(I) complex with only minor unpaired spin transfer onto the isonitrile. For aliphatic isonitriles, the selective R-CN bond cleavage occurs and yields stoichiometric mixtures of alkyl iron(II) and cyanido iron(II) complexes. Attempts to isolate presumed (iso)nitrile radical anions void of 3d-metal coordination give for the reaction of an aromatic isonitrile with KC8 facile reductive coupling to the corresponding diamido acetylene.

Cationic Tetrylene-Iron(0) Complexes: Access Points for Cooperative, Reversible Bond Activation and Open-Shell Iron(-I) Ferrato-Tetrylenes.

The open-shell cationic stannylene-iron(0) complex 4 (4=[PhiP DippSn⋅Fe⋅IPr]+ ; PhiP Dipp={[Ph2 PCH2 Si(i Pr)2 ](Dipp)N}; Dipp=2,6-i Pr2 C6 H3 ; IPr=[(Dipp)NC(H)]2 C:) cooperatively and reversibly cleaves dihydrogen at the Sn-Fe interface under mild conditions (1.5 bar, 298 K), in forming bridging hydrido-complex 6. The One-electron oreduction of the related GeII -Fe0 complex 3 leads to oxidative addition of one C-P linkage of the PhiP Dipp ligand in an intermediary Fe-I complex, leading to FeI phosphide species 7. One-electron reduction reaction of 4 gives access to the iron(-I) ferrato-stannylene, 8, giving evidence for the transient formation of such a species in the reduction of 3. The covalently bound tin(II)-iron(-I) compound 8 has been characterised through EPR spectroscopy, SQUID magnetometry, and supporting computational analysis, which strongly indicate a high localization of electron spin density at Fe-I in this unique d9 -iron complex.

Taming the stilbene radical anion.

Radical anions appear as intermediates in a variety of organic reductions and have recently garnered interest for their role as mediators for electron-driven catalysis as well as for organic electron conductor materials. Due to their unstable nature, the isolation of such organic radical anions is usually only possible by using extended aromatic systems, whereas non-aromatic unsaturated hydrocarbons have so far only been observed in situ. We herein report the first isolation, structure and spectroscopic characterization of a simple aryl substituted alkene radical anion, namely that of stilbene (1,2-diphenyl ethylene), achieved by encapsulation between two [K{18c6}] cations. The formation of the radical anion is accompanied by Z → E isomerization of the involved double bond, also on a catalytic scale. Employing the linear iron(i) complex [Fe(NR2)2]- as a reductant and coordination site also allows for this transformation, via formation of an iron(ii) bound radical anion. The use of the iron complex now also allows for Z → E isomerization of electron richer, simple alkenes bearing either mixed alkyl/aryl or even bis(alkyl) substitution.