Remarkable reactions of (eta(4)-1-azadiene)Fe(CO)(3) complexes with aryllithium reagents. Syntheses and structures of novel chelated furanyl-coordinated alkoxy(amino)carbeneiron, eta(4)-azadiene-coordinated 17e acyliron, and iron inner salt complexes

摘要

The reactions of a (eta (4)-1-azadiene)Fe(CO)(3) complex, [(eta (4)-C4H3OCH=CHCH=NC6H11)Fe-(CO)(3)] (1), with aryllithium reagents, ArLi (Ar = C6H5, p-CH3C6H4, o-CH3OC6H4, p-CH3-OC6H4, p-CF3C6H4), in ether at low temperature followed by alkylation with Et3OBF4 in aqueous solution at 0 degreesC or in CH2Cl2 at -60 degreesC gave novel chelated furanyl-coordinated alkoxy(amino)carbeneiron complexes [{eta (4)-C4H3OCH=CHCH(Ar)N(C6H5)C(OC2H5)=}Fe(CO)(2)] (4, Ar = C6H5; 5, Ar = p-CH3C6H4; 6, Ar = o-CH3OC6H4; 7, Ar = p-CH3OC6H4; 8, Ar = p-CF3C6H4). The analogous reactions of compounds [(eta (4)-C4H3OCH=CHCH=NC6H11)Fe(CO)(3)] (2) and [(eta (4)-C6H5CH=CHCH=NC6H11)Fe(CO)(3)] (3) with ArLi (Ar = C6H5, o-, m-, p-CH3C6H4) afforded novel eta (4)-azadiene-coordinated 17e acyliron complexes [{eta (4)-(CHOCH)-H-4-O-3=CHCH= NC6H11}Fe(CO)(2)(COAr)] (9, Ar = C6H5; 10, Ar = o-CH3C6H4; 11, Ar = m-CH3C6H4; 12, Ar = p-CH3C6H4) and [(eta (4)-C6H5CH=CHCH=NC6H11)Fe(CO)(2)(COAr)] (15, Ar = C6H5; 16, Ar = p-CH3C6H4), respectively. Unexpectedly, 2 reacts similarly with p-CH3-OC6H4Li and p-CF3C6H4Li to yield novel eta (2)-azadiene-coordinated acyliron inner salt complexes [{eta (2)-C4H3O-CH=CHCH=N(C2H5)C6H11}Fe(CO)(3)(COAr)] (13, Ar = p-CH3-OC6H4; 14, Ar = p-CF3C6H4). Analogous acyliron inner salt complex [{eta (2)-C6H5CH=CHCH=N(C2H5)-C6H11}Fe(CO)(3)(COC6H4CH8-p)] (18) was also obtained from the reaction of 3 with p-CH3-OC6H4Li. However, similar reactions of 3 with ArLi (Ar = o-CH3OC6H4; 21, Ar = p-CF3C6H4). The structures of 6, 10, 13 and 18 have been established by X-ray diffraction studies. [References: 28]