Addition of protic nucleophiles to alkynyl methoxy carbene ligands in diiron complexes

摘要

Different protic nucleophiles (i.e. Ph2C=NH, PhSH, MeCO2H, PhOH) can be added to the C equivalent to C bond of [Fe-2{mu-CN(Me)(Xyl)}-(mu-CO)(CO){C(OMe)C equivalent to CTol}(CP)(2)][SO3CF3] (1), affording new diiron alkenyl methoxy carbene complexes. The additions of Ph2C=NH and MeCO2H are regio and stereoselective, resulting in the formation of the 5-aza-1-metalla-1,3,5-hexatriene [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(OMe)C beta H=C-gamma(Tol)(N=CPh2)}(CP)(2)][SO3CF3](2), and the 2-(acyloxy)alkenyl methoxy carbene complex [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(OMe)C beta H=C-gamma(Tol)OC(O)Me)}(CP)(2)][CF3SO3] (5); the E isomer of the former and the Z of the latter are formed exclusively. Conversely, the addition of PhSH is regio but not stereoselective; thus, both the E and Z isomers of [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(OMe)C beta H=C-gamma(Tol)(SPh)}(CP)(2)][SO3CF3](3) are formed in comparable amounts. Compounds 3 and 5 are demethylated upon chromatography through Al2O3, resulting in the formation of the acyl complexes [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(O)C beta H=C-gamma(Tol)(SPh)}(Cp)(2)](4) and [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(O)C beta H=C-gamma(Tol)OC(O)Me}(CP)(2)](6), respectively, both with a Z configured C-beta=C-gamma bond. Finally, the reaction of 1 with PhOH proceeds only in the presence of an excess of Et3N affording the 2-(alkoxy)alkenyl acyl complex [Fe-2{mu-CN(Me)(Xyl)}(mu-CO)(CO){C-alpha(O)C beta H=C-gamma(Tol)(OPh)}(CP)(2)](7). The crystal structures of 4 center dot CH2Cl2 and 7 center dot 0.5CH(2)Cl(2) have been determined by X-ray diffraction experiments.