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Amidino-complexes of iron(II) and (III) |
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| Authors: | JAndrew Clark Melvyn Kilner Antoni Pietrzykowski | |
| Institution: | Department of Chemistry, University of Durham, South Road, Durham City, DH1 3LE, U.K. | |
| Abstract: | Lithioamidines {R′N(Li)C(R)NR′, I; R = CH3, R′ = C6H5, p-CH3,C6H4} react with iron(III) chloride ![/></figure> in monoglyme to produce navy-blue, high spin Fe{R′NC(R)NR′}<sub>3</sub> complexes which are extremely air and moisture sensitive. The corresponding reaction when R = R′ = C<sub>6</sub>H<sub>5</sub> produces a soluble red complex and an air-stable green complex, whereas when R = H, R′ = C<sub>6</sub>H<sub>5</sub> and R = R′ = C<sub>6</sub>H<sub>5</sub> and the reaction is started at ca. ?20°, red and green complexes respectively are formed. Though all the complexes are formulated Fe{R′NC(R)NR′}<sub>3</sub>, their properties reflect association through bridging amidino-groups. Iron(II) chloride reacts with I(R = CH<sub>3</sub>, R′ = p-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>) to form two complexes, one crimson and soluble in organic solvents, and one brown and insoluble, which are fomulated Fe{R′NC(R)NR′}<sub>2</sub>]<sub>n</sub>. The iron(III) complexes failed to react with, or were decomposed by, a variety of reducing, electrophilic and nucleophilic reagents, though blue Fe{p-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>NC(CH<sub>3</sub>)N-p-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>}<sub>3</sub> reacts readily with nitric oxide to form a purple addition complex from which the N-nitroso-compound p-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub>NC(CH<sub>3</sub>)N(NO)-p-CH<sub>3</sub>C<sub>6</sub>H<sub>4</sub> was obtained in high yield. Treatment of the corresponding brown iron(II) complex with nitric oxide gave no reaction.</td>
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| Keywords: | Author to whom correspondence should be addressed | |
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