Functional Ruthenium(II) Allenylidene and Diynyl (Arene) Derivatives Formed by Activation of a Diyne via a Ru:C:C:C:C:CR2 Intermediate
作者:Daniel Peron、Antonio Romero、Pierre H. Dixneuf
DOI:10.1021/om00007a036
日期:1995.7
The activation of the diyne HC=CC=CC(OSiMe(3))Ph(2) (II) by a variety of RuCl2(PR(3))(C-6-Me(6)) complexes 1 [PR(3) = PMe(3)(a), PMe(2)Ph (b), PMePh(2)(c)], in the presence of the salt NaPF6, selectively leads either to [L(n)Ru=C(OMe)CH=C=C=CR(2)]PF6 (3), [L(n)Ru=C=C=C(OR)-CH=CR(2)]PF6 (4-6), [L(n)Ru=C=C=C(NR'(2))CH=CR(2)]PF6 (7), or [L(n)Ru-C=CC=CC(OSiMe(3))-Ph(2)]PF6 (8), (L(n)Ru = RuCl(PR(3))(C(6)Me(6))). In methanol 1a leads to the buta-1,a,3-trienylcarbene complex 3 and the 3-alkenylallenylidene derivative 4a. In ethanol and 2-propanol the complexes containing the 3-alkenylallenylidene moiety 5a-c and 6a-c are generated from 1a-c. In the presence of HNPh(2) the derivatives [L(n)Ru=C=C=C(NPh(2))CH=CPh(2)]PF6 (7a-c) are obtained, whereas in the presence of (HNPr2)-Pr-i, NEt(3) or, Bu(t)NH(2) and NaPF6 the diynyl derivatives 8a-c are selectively produced. The protonation with HBF4 of the diynyl complexes 8 in the presence of alcohol or diphenylamine is shown to displace the OSiMe(3) group and generate (3-alkenylallenylidene)ruthenium derivatives 6-7*. The activation of the diyne II by complexes 1 and NaPF6 can be rationalized in terms of the formation of the electrophilic penta-1,2,3,4-tetraenylidene intermediate [(C(6)Me(6))(PR(3))CI Ru=C=C=C=C=CPh(2)](+) (2), which is reactive toward weak nucleophiles.