Hydrido-Silyl-Komplexe, IV [1]. Strukturelle Änderungen in Hydrido-Silyl-Komplexen infolge Si-H-Wechselwirkung; Strukturvergleich von (π-CH3C5H4)(CO)2Mn(H)SiCl3 und trans-(π-CH3C5H4)(CO)2Mn(SiCl3)2 / Hydrido Silyl Complexes, IV [1]. Structural Changes in Hydrido Silyl Complexes Due to Si-H Interaction; Comparison of the Structures of (π-CH3C5H4)(CO)2Mn(H)SiCl3 and trans-(π-CH3C5H4)(CO)2Mn(SiCl3)2

Abstract

Abstract The main difference between the structures of MeCp(CO)2Mn(H)SiCl3 (1) and MeCp(CO)2Mn(SiCl3)2 (2) is that in 1 the SiCl3 ligand is tilted relative to the Mn-Si vector, due to Mn-H-Si three-center two-electron bonding. Mn-Si: 225.4(1) in 1, 232.0(2) pm in 2. Comparison of the structures of MeCp(CO)2Mn(H)SiR3 complexes shows that the Mn-Si distance and the tilt angle of the SiR3 group increases as Si-H interaction increases. A stereochemical pathway of the oxidative addition of HSiR3 to the CpMn(CO)3 fragment is suggested.