An unusual product distribution from the reaction of Pd(eta(3)-1-PhC3H4)(eta(5)-C5H5) with a deficiency of PPh3 in the presence of bromobenzene

作者：Zhang Xin; Borjian Sogol; Baird Michael C^*

来源：Transition Metal Chemistry, 2015, 40(2): 125-129.

DOI：10.1007/s11243-014-9897-7

Reactions of Pd(eta(3)-1-PhC3H4)(eta(5)-C5H5) (I) with PPh3 (1:1 ratio) in the presence of excess bromobenzene result in the formation of Pd(eta(5)-C5H5)(eta(1)-PhC3H4)(PPh3) (II), syn- and anti-isomers of the dinuclear species Pd2L2(mu-C5H5)(mu-PhC3H4) (IIIa, b), the phenyl compound PdPh(eta(5)-C5H5)(PPh3) (IV), the dinuclear species Pd2L2(mu-Br)(mu-anti-PhC3H4) (V) and an organic compound, trans-1,3-diphenylpropene. Not observed are trans-PdBrPh(PPh3)(2) and [PdBrPh(PPh3)](2), the anticipated products of oxidative addition of bromobenzene to Pd(0)-PPh3 species, and thus, the types of products formed are generally very different from those obtained elsewhere with other phosphines. Compounds IV and V are found to be very stable at high temperature and to be relatively poor catalysts for e.g., the amination of bromoanisole by morpholine in the presence of sodium t-butoxide.

• 出版日期2015-3