Cyclic oxycarbene and vinylidene complexes of ruthenium with (P-P) and (N-N) type ligands

摘要

trans-[(dppM)(2)ClRu=C(CH2)(3)O](+) (2) (dppm = Ph2PCH2PPh2) and trans-[(dppm)(2)ClRu=C(CH2)(2)CH(CH)(3)O](+) (3) cations were obtained from the reaction of cis-[RuCl2(dppm)(2)] (1) with 3-butyn-1-ol and 4-pentyn-2-ol, respectively. cis-Dichlororuthenim complex [RuCl2((dppene)(bpy)] (4) (dppene = Ph2PCHCHPPh2, bpy = 2,2'-bipyridyl) also reacts with terminal alkynes e.g. 4-pentyn-2-ol and phenylacetylene to give cis-chloro-(oxycarbene)[(dppene)(bpy)ClRu=C(CH2)(2)CH(CH)(3)O](+) (5) and cis-chloro(vinylidene)[(dppene)(bpy)ClRu=C=CHPh](+) (6) cations. cis-[RuCl2(bpy)(2)] (7) also react with 4-pentyn-2-ol to give dioxacyclic carbene dication cis-[(bpy)(2)Ru=(C(CH2)(2)CH(CH)(3)O](2)(2+) (8) In the reaction of RuCl2(PPh3)(3) (9) with 3-butyn-1-ol the dimer [(PPh3)(2)ClRu=C(CH2)(3)O](2)(2+) (10) was obtained. The new synthesis method of 1 and cis-[RuCl2(dppm)(2)].2MeOH (1a) is also presented. These complexes have been fully characterized by IR, H-1, C-13{H} and P-31{H} NMR) and single crystal X-ray diffraction for 2, 3, 5 and 1a. The catalytic activity of 10 in reactions of ROMP of norbornene was also studied. (C) 2002 Elsevier Science B.V. All rights reserved. [References: 79]