Abstract: | Hydrido Silyl Complexes. V. Structural Changes in Hydrido Silyl Complexes Due to Si? H Interaction; Comparison between the Structures of (π-CH3C5H4)(CO)2Mn(H)SiR3 and Analogous (π-C5H5)(CO)2FeSiR3 Complexes The structures of the complexes Cp(CO)2FeSiFPh2 ( 2a ) and Cp(CO)2FeSiCl3 ( 2b ), containing ?normal”? metal-silicon bonds, are compared with the known structures of the complexes MeCp(CO)2Mn(H)SiFPh2 ( 1a ) and MeCp(CO)2Mn(H)SiCl3 ( 1b ), containing Mn? H? Si three-center bonds. 2a crystallizes in space group P21/c, a = 805.8(3), b = 1417.5(6), c = 1498.2(4) pm, β = 90.99(3)°, 2b in space group P21/n, a = 817(1), b = 1244(1), c = 1142(1)pm, β = 99.9(1)°. In 2a gauche conformation in respect to the Fe? Si bond is found; in 2b the silylligand is rotated 12° around the Fe? Si axis out of a staggered conformation. Possible reasons for the unsymmetrical conformations are discussed. Lengthening of the Fe? Si distance from 221.6(1)pm in 2b to 227.8(1) pm in 2a corresponds to the expected increase in the bond radius of silicon due to exchange of the substituents at silicon. Additional lengthening of the Mn? Si distance by about 3.5 pm in 1a compared with 1b is attributed to the increased delocalization of the Mn? H? Si bond in 1a . |