Reactions of [Cp*Ru(H2O)(NBD)](+) with dihydrogen, silanes, olefins, alkynes, and allenes

Submitted by Jun Zhu on Thu, 10/31/2013 - 23:44
Authors: 
Peng Xue, Jun Zhu, Sheng Hua Liu, Xin Huang, Weng Sang Ng, Herman H. Y. Sung, Ian D. Williams, Zhenyang Lin*, Guochen Jia*
Journal: 
Organometallics
Year: 
2006
Volume: 
25
FirstPage-LastPage: 
2344–2354
Keywords: 
Dihydrogen
Silanes
Olefins
Alkynes
Allenes
TOC: 
Abstract: 

Formal [2+2+2] addition reactions of the NBD ligand in [Cp*Ru(H2O)(NBD)]BF4 (NBD = norbornadiene) with H-2, Ph3SiH, ArCH=C=CH2, and RC=-CPh were observed. In contrast, olefins such as styrene and NBD do not undergo similar [2+2+2] addition reactions with [Cp*Ru(H2O)(NBD)]BF4. [Cp*Ru(H2O)(NBD)]BF4 reacts with H-2 in benzene to give [Cp*Ru(eta(6)-C6H6)]BF4 and nortricyclene. Similarly, [Cp*Ru(H2O)(NBD)]BF4 reacts with Ph3SiH to give [Cp*Ru(eta(6)-C6H5SiPh2OH)]BF4 and nortricyclene. Treatment of [Cp*Ru(H2O)(NBD)]BF4 with styrene produces [Cp*Ru(eta(6)-C6H5-CH=CHC7H9)]BF4, [Cp*Ru(eta(6)-C6H5-CH=CH2)]BF4, C6H5-CH=CH-C7H9, and Cp*Ru(eta(5) -C5H4-C9H11). The latter complex is also produced from the reaction of [Cp*Ru(H2O)(NBD)]BF4 with NBD. Treatment of [Cp*Ru(H2O)(NBD)]BF4 with ArCH=C=CH2 produces [Cp*Ru(eta(6)-Ar-C10H11)]BF4. Reactions of [Cp*Ru(H2O)- (NBD)]BF4 with RC=CC6H5 (R = Ph, Me) give [Cp*Ru(eta(6)-C6H5-C10H8R)]BF4. The reaction pathways of the coupling reactions have been studied by computational chemistry.

Doi: 
10.1021/om0600285