Organoirons

The discussion herein is limited to several simple compounds that are stable, readily available, and used as starting materials for many other organoiron compounds. 

As mentioned earlier, the possible products of the -complexes include ring-opened structures. This includes isomer 181 and some of its derivatives, for example, 187,188,196,197, 203, and 204, as well as the products of interaction with organoiron, 180,191, and 194, and organocobalt, 199,200, and 201, compounds. They have already been discussed together with the variously characterized V-complexes. Examples of the ring-opening reactions based on the -q- and ri -species are given next. 

The case of C-coordinated oxazole, 21, was reported in organoiron chemistry (89JOM(372)287). Another example involves the interaction of the cyano complexes [M(CN)(Cp)(dppe)] (M = Fe, Ru) or [(rj -Cp)Fe(dppe)(CNH)]Br with gem-dicyanoepoxide to afford the oxazol-2-yl complexes with the C-coordination mode (96JCS(D)3231). 

Organoiron chemistry offers the C-coordination mode, carbene series, ring opening and detelluration. Organoruthenium and especially organoosmium species are sometimes peculiar along with the classical cases of N-coordination and carbene formation, C,N- and S,N-cases can be traced. 

The reaction proceeds by an ET pathway giving the I9e organoiron radical cation and the organic radical R which couple in the cage after escape ofX. The cationic Fe1 intermediate is noted at low temperature by its characteristic purple color and the classical spectrum of Fe1 species with rhombic distortion (g = 2.091, 2.012, 2.003 at —140 °C in acetone) before collapse to the orange substituted cyclohexa-dienyl Fe11 complexes. 

Six-coordinate organoiron porphyrin nitrosyl complexes, Fe(Por)(R)(NO), were prepared from Fe(Por)R (Por = OEP or TPP R = Me, n-Bu, aryl) with NO gas. The NMR chemical shifts were typical of diamagnetic complexes, and the oxidation state of iron was assigned as iron(ll). ... 

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