Diruthenium Carbido Complexes as N-Heterocyclic Carbene Like C-Donor Ligands to Group 11 Metals
Diruthenium Carbido Complexes as N-Heterocyclic Carbene Like C-Donor Ligands to Group 11 Metals
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作为第 11 族金属的 N-杂环卡宾类 C 供体配体的二钌碳化物配合物
DOI：
10.1021/acs.organomet.7b00229
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发表时间：
2017
期刊：
影响因子：
2.8
通讯作者：
Matsuzaka Hiroyuki
中科院分区：
文献类型：
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作者：
Takemoto Shin;Tsujita Masayuki;Matsuzaka Hiroyuki
在CuCN、AgOTf或Au(SMe2)存在下，二Ruμ-亚甲基配合物[(Cp*Ru)2(μ-NtBu)(μ-CH)][BF4](Cp*=η5-C5Me5)与2当量的KN(SiMe3)2发生去质子化反应得到了三方平面桥联碳化物配合物[(Cp*Ru)2(μ-NtBu)(μ3-C)M{N(SiMe3)2}](M=Cu4)，Ag(5)，Au(6)。对络合物4和6进行了结晶学表征。这些化合物的M-C键与杂环卡宾衍生物(NHC)M{N(SiMe_3)_2}(M=铜和Au)的M-C键非常相似，说明碳化二Ru配体[(Cp*Ru)2(μ-NtBu)(μ-C)]与非杂环卡宾的M-C键相似。4与2，6-二叔丁基苯酚反应，可通过二硅氮化物的质子化交换进行衍生化反应，得到芳氧基配合物[(Cp*Ru)2(μ-NtBu)(μ3-C)Cu(Oar)](7；Ar=2，6-tBu2C6H3)，并对其结构进行了表征。用计算方法研究了碳化二Ru配体的电子给体能力和空间构型。
Deprotonation of the diruthenium μ-methylidyne complex [(Cp*Ru)2(μ-NtBu)(μ-CH)][BF4] (Cp* = η5-C5Me5) with 2 equiv of KN(SiMe3)2in the presence of CuCN, AgOTf, or AuCl(SMe2) afforded the trigonal planar bridging carbido complexes [(Cp*Ru)2(μ-NtBu)(μ3-C)M{N(SiMe3)2}] (M = Cu (4), Ag (5), and Au (6)). Complexes4and6were characterized crystallographically. The M–C bonding in these complexes showed considerable similarity with that in theN-heterocyclic carbene (NHC) derivatives (NHC)M{N(SiMe3)2} (M = Cu and Au), illustrating the analogy between the diruthenium carbido ligand [(Cp*Ru)2(μ-NtBu)(μ-C)] and NHCs. The reaction of4with 2,6-di-tert-butylphenol allowed derivatization via protonolytic exchange of the disilazide moiety, yielding the aryloxo complex [(Cp*Ru)2(μ-NtBu)(μ3-C)Cu(OAr)] (7; Ar = 2,6-tBu2C6H3), which was also structurally characterized. The electron donor ability and steric bulkiness of the diruthenium carbido ligand were studied by computational methods.