A New Approach to Directly Synthesize (eta(5)-C5H4R)Fe(CO)(2)SiR '(3) by Reaction of Cyclopentadienes with Pentacarbonyliron and Hydrosilanes

作者：Gu, Guangna; Luo, Haiou; Sun, Huailin^*

来源：Organometallics, 2014, 33(7): 1710-1714.

DOI：10.1021/om500066y

• TRANSITION-METAL-COMPLEXES
• SILICON-SILICON
• MOLECULAR-STRUCTURE
• DISSOCIATIVE LOSS
• IRON COMPLEXES
• CARBON BONDS
• DERIVATIVES
• PHOTOCHEMISTRY
• SI
• FP

A new approach to the direct synthesis of Fe Si-bonded complexes (eta(5)-C5H4R)Fe(CO)(2)SiR'(3) (1) by the reaction of cyclopentadienes C5H5R (2) with pentacarbonyliron in the presence of hydrosilanes R'3SiH (5) has been developed. Thus, when the reaction of 2 and pentacarbonyliron in refluxing p-xylene was performed in the presence of 5, the desired complexes were successfully obtained in good yields, providing a simple one-step synthetic route to obtain 1 from the readily available starting materials, wherein the substituents R and R' could vary over a wide range: C5H5R = C3H5SiMe2SiMe3, R'(3) = Ph-3 (la); C5H5R = C5H5SiMe2SiMe2Ph, R'(3) = Ph-3 (1h); C5H5R = C5H5SiMe2SiMePh2, = Ph-3 (1f); C5H5R = C5H5SiMe2SiPh3, R'(3) = Ph-3 (1d); C5H5R = C(5)H(5)SiPh(2)StPh(3), R'(3) = Ph-3 (1e); C5H5R = C5H5SiMe3, R'(3) = Ph-3 (1o; C5H5R = C5H6, R'(3) = Ph-3 (1g);C5H5R = CsHsMe, R'(3) = Ph3 (1h);C5H5R = C5H5CH2Ph, R'(3) = Ph-3 (1i);C5H5R = MeC5H4SiM03, R'(3) = Ph3 (10; C5H5R=C9H8, R'(3) = Ph3 (1k);C5H5R = C5H5SiMe2SiMe2Ph, R'(3) = Me2Ph (1i); C5H5R = C5H5SiMe2Ph3, R'(3) = Me2Ph (1m); C5H5R = C(5)H(5)SiPh(2)StPh(3), R'(3) = Me2Ph (In);C5H5R = C5H5CH2Ph, R'(3) = MezPh (10). A plausible mechanism involving interception of coordinatively unsaturated iron species (eta(4)-C5H5R)Fe(CO)(2) by oxidative addition of the Si H bond is believed to be responsible for the preferred formation of the desired product.

• 出版日期2014-4-14
• 单位南开大学