Ligand effect on the insertion reactions of allenes with MHCl(CO)(PPh3)3and MHCl(PPh3)3 (M = Ru, Os)

被引：31

作者：

Bai, Tao

Zhu, Jun

Xue, Peng

Sung, Herman Ho-Yung

Williams, Ian Duncan

Ma, Shengming

Lin, Zhenyang

Jia, Guochen

机构：

[1] Chinese Acad Sci, Shanghai Inst Organ Chem, State Key Lab Organomet Chem, Shanghai 200032, Peoples R China

[2] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China

来源：

ORGANOMETALLICS | 2007年 / 26卷 / 23期

关键词：

D O I：

10.1021/om700629x

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Treatment of RuHCl(CO)(PPh3)(3) with CH2=C=CHCO2Me gives the allyl complex Ru(77 3 -CH2CHCHCO2Me)CI(CO)(PPh3)(2). The analogous allyl complexes Os(eta(3)-CH2CHCHR)Cl(CO)(PPh3)(2) (R = Ph, CH2Ph) are also produced from the reactions of OsHCI(CO)(PPh3)(3) with CH2=C=CHR. In contrast, MHCl(PPh3)(3) (M = Ru, Os) react with CH2=C=CHR to give the vinyl complexes MCl((C(CH3)=CHR)(CH2 C=CHR)(PPh3)(2) (M = Ru, R = CMe3, M = Os, R = CMe3, Ph, CO2Et). The difference in the reaction pathways for the reactions of allenes with MHCl(CO)(PPh3)(3) and MHCl(PPh3)(3) (M = Ru, Os) has been studied by computational chemistry. The theoretical study shows that the observed different reactivity can be related to the significant difference in the electron density increase at the central carbon of the allene ligand upon coordination to the metal fragments.

引用

页码：5581 / 5589

页数：9

共 133 条

[11] Highly chemo-, regio-, and stereoselective [3+2]-cyclization of activated and deactivated allenes with alkenyl Fischer carbene complexes:: A straightforward access to alkylidenecyclopentanone derivatives [J].