Coordinatively Unsaturated Hydridoruthenium(II) Complexes of N-Heterocyclic Carbenes
Coordinatively Unsaturated Hydridoruthenium(II) Complexes of N-Heterocyclic Carbenes
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DOI：
10.1021/om034178g
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发表时间：
2004
期刊：
影响因子：
2.8
通讯作者：
K. Abdur-Rashid;Terry Fedorkiw;A. Lough;R. Morris
中科院分区：
文献类型：
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作者：
K. Abdur-Rashid;Terry Fedorkiw;A. Lough;R. Morris
以RuHCl(R-binap)(R,R-dach)/KOtBu在甲苯中催化相应的二亚胺加氢制备的二胺为原料，合成了含有R =甲酰基（SIMes）， 2,6-二异丙基苯基的饱和咪唑啉-2-基化合物RNC3H4NR。配体IMes （MesNC3H2NMes）和SIMes分别与RuHCl(PPh3)3反应生成RuH(SIMes-H)(PPh3)2(1)和RuH(IMes-H)(PPh3)2(2)，其中邻位Ar−CH3基团的C−H键发生环金属化反应。RuHCl(PPh3)3与ItBu （tBuNC3H2NtBu）反应生成ItBu·HCl和一种红色溶液，该溶液与H2反应生成二氢化物Ru(H)2(ItBu)(PPh3)2作为两种异构体3a（反式PPh3配体）和3b（顺式PPh3）的混合物。这些同分异构体有一个来自甲基的C - H键。同分异构体3a中的配位叔丁基发生了一种有趣的雨刷式交换，通过VT核磁共振在溶液中监测到其自由激活能为11.8 kcal/mol。2与CO在20℃下反应生成(OC-34)-…
The saturated imidazolin-2-ylidene compounds RNC3H4NR, with R = mesityl (SIMes), 2,6-diisopropylphenyl, were synthesized by use of diamines that were prepared by the hydrogenation of the corresponding diimines catalyzed by RuHCl(R-binap)(R,R-dach)/KOtBu in toluene. The ligands IMes (MesNC3H2NMes) and SIMes react with RuHCl(PPh3)3 to give RuH(SIMes-H)(PPh3)2 (1) and RuH(IMes-H)(PPh3)2 (2), respectively, where there is cyclometalation of a C−H bond of an ortho Ar−CH3 group. The reaction of RuHCl(PPh3)3 with ItBu (tBuNC3H2NtBu) produces ItBu·HCl and a red solution that, upon reaction with H2, produces the dihydride Ru(H)2(ItBu)(PPh3)2 as a mixture of the two isomers 3a (trans PPh3 ligands) and 3b (cis PPh3). These isomers have an agostic C−H bond from a methyl group. There is an interesting windshield wiper exchange of coordinated tert-butyl groups occurring in isomer 3a, as monitored in solution by VT NMR with a free energy of activation of 11.8 kcal/mol. The reaction of 2 with CO at 20 °C produces (OC-34)-...