The electronic structure of three single atom bridged diiron octapropylporphyrazine complexes (FePzPr8)2X having Fe(III)-O-Fe(III), Fe(III)-N-Fe(IV) and Fe(IV)-C-Fe(IV) structural units was investigated by Mössbauer spectroscopy and DFT calculations. In this series, the isomer shift values decrease whereas the values of quadrupole splitting become progressively greater indicating the increase of covalency of Fe-X bond in the µ-oxo -µ-nitrido -µ-carbido row.The Mössbauer data point to low spin systems for the three complexes and calculated data with B3LYP-D3 show a singlet state for µ-oxo and µ-carbido and a doublet state for µ-nitrido complexes. An excellent agreement was obtained between B3LYP-D3 optimized geometries and X-ray structural data. Among (FePzPr8)2X complexes, µ-oxo diiron species showed a higher reactivity in the cyclopropanation of styrene by ethyl diazoacetate to afford a 95 % product yield with 0.1 mol% catalyst loading. A detailed DFT study allowed to get insight into electronic structure of binuclear carbene species and to confirm their involvement into carbene transfer reaction.
A μ-carbido diruthenium(iv) phthalocyanine complex was prepared for the first time from the free-base octabutoxyphthalocyanine by direct metalation with Ru(CO). The first examples of the catalytic activity of Ru(iv) binuclear phthalocyanines were demonstrated by the cyclopropanation of aromatic olefins and carbene insertion into the N-H bonds of aromatic or aliphatic amines with turnover numbers of 680-1000 and 580-1000, respectively.
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