Bagh Bidraha, McKinty Adam M, Lough Alan J, Stephan Douglas W
Department of Chemistry, University of Toronto, 80 St George St, Toronto, Ontario, CanadaM5S3H6.
Dalton Trans. 2015 Feb 14;44(6):2712-23. doi: 10.1039/c4dt03156c.
Silver(i) 1,2,3-triazol-5-ylidenes [(RCH(2)C(2)N(2)(NMe)Ph)(2)Ag][AgCl(2)] (R = Ph 3a, C(6)H(2)iPr(3) 3b, C(6)H(2)Me(3) 3c) and [(PhCH(2)C(2)N(2)(NMe)R)(2)Ag][AgCl(2)] (R = C(6)H(4)Me 3d, C(6)H(4)CF(3) 3e) were synthesized and subsequently treated with RuHCl(PPh(3))(3) and RuHCl(H(2))(PCy(3))(2). The reaction 3a of with RuHCl(PPh(3))(3) gave RuHCl(PPh(3))(2)(PhCH(2)C(2)N(2)(NMe)Ph) (4a1) as the minor product and the cyclometalated complex RuCl(PPh(3))(2)(PhCH(2)C(2)N(2)(NMe)C(6)H(4)) (4a2) as the major product. However, similar reaction with 3b selectively formed the cyclometalated complex RuCl(PPh(3))(2)((C(6)H(2)iPr(3))CH(2)C(2)N(2)(NMe)C(6)H(4)) (4b2). Similarly the silver(i) triazolylidenes 3a and 3b were reacted with RuHCl(H(2))(PCy(3))(2); gave RuHCl(PCy(3))(2)(PhCH(2)C(2)N(2)(NMe)Ph) (5a2), RuCl(PCy(3))(2)(PhCH(2)C(2)N(2)(NMe)C(6)H(4)) (5a2) and RuCl(PCy(3))(2)((C(6)H(2)iPr(3))CH(2)C(2)N(2)(NMe)C(6)H(4)) (5b2), respectively. Species 3c, 3d and 3e resulted in the cyclometalated complexes (5c2, 5d2 and 5e2) as the major products as well as the ruthenium-hydride complexes (5c1, 5d1 and 5e1) as the minor products. The cyclometalated species are derived from the ruthenium-hydride complexes via C(sp(2))-H activation. These Ru-complexes were shown to act as hydrogenation catalyst precursors for olefinic substrates including those containing a variety of functional groups.
合成了银（I）1,2,3 - 三唑 - 5 - 亚基[（RCH(2)C(2)N(2)(NMe)Ph)(2)Ag][AgCl(2)]（R = Ph 3a、C(6)H(2)iPr(3) 3b、C(6)H(2)Me(3) 3c）和[（PhCH(2)C(2)N(2)(NMe)R)(2)Ag][AgCl(2)]（R = C(6)H(4)Me 3d、C(6)H(4)CF(3) 3e），随后用RuHCl(PPh(3))(3)和RuHCl(H(2))(PCy(3))(2)处理。3a与RuHCl(PPh(3))(3)的反应产生了次要产物RuHCl(PPh(3))(2)(PhCH(2)C(2)N(2)(NMe)Ph)（4a1）和主要产物环金属化配合物RuCl(PPh(3))(2)(PhCH(2)C(2)N(2)(NMe)C(6)H(4))（4a2）。然而，与3b的类似反应选择性地形成了环金属化配合物RuCl(PPh(3))(2)((C(6)H(2)iPr(3))CH(2)C(2)N(2)(NMe)C(6)H(4))（4b2）。同样，银（I）三唑亚基3a和3b与RuHCl(H(2))(PCy(3))(2)反应；分别得到RuHCl(PCy(3))(2)(PhCH(2)C(2)N(2)(NMe)Ph)（5a2）、RuCl(PCy(3))(2)(PhCH(2)C(2)N(2)(NMe)C(6)H(4))（5a2）和RuCl(PCy(3))(2)((C(6)H(2)iPr(3))CH(2)C(2)N(2)(NMe)C(6)H(4))（5b2）。物种3c、3d和3e分别以主要产物环金属化配合物（5c2、5d2和5e2）以及次要产物钌氢配合物（5c1、5d1和5e1）的形式产生。环金属化物种是通过C(sp(2)) - H活化从钌氢配合物衍生而来的。这些钌配合物被证明可作为包括那些含有各种官能团的烯烃底物的氢化催化剂前体。
