Metal-Templated Hydrogen Bond Donors as “Organocatalysts” for Carbon–Carbon Bond Forming Reactions: Syntheses, Structures, and Reactivities of 2-Guanidinobenzimidazole Cyclopentadienyl Ruthenium Complexes
Metal-Templated Hydrogen Bond Donors as “Organocatalysts” for Carbon–Carbon Bond Forming Reactions: Syntheses, Structures, and Reactivities of 2-Guanidinobenzimidazole Cyclopentadienyl Ruthenium Complexes
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金属模板氢键供体作为碳-碳键形成反应的“有机催化剂”：2-胍基苯并咪唑环戊二烯基钌配合物的合成、结构和反应性
DOI：
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发表时间：
2014
期刊：
影响因子：
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通讯作者：
J. Gladysz
中科院分区：
文献类型：
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作者：
A. Scherer;T. Mukherjee;F. Hampel;J. Gladysz
2-胍基苯并咪唑（GBI）与（η_5-C_5H_5）Ru（PPh_3）_2（Cl）在三甲苯中反应，生成螯合物[（η_5-C_5H_5）Ru（PPh_3）（GBI）]+Cl-（1+Cl-; 96%）。随后的阴离子复分解产生BF 4-、PF 6-和BArf-（B（3，5-C6 H3（CF 3）2）4-）盐（77-85%）。与CO反应得到羰基配合物[（η_5-C_5 H_5）Ru（CO）（GBI）]+X ~-（2+X ~-; X ~- = Cl ~-，BF ~ 4 ~-，PF ~ 6 ~-，BAr ~-; 87-92%）。最后三种盐也可以通过2+Cl-（77-87%）的阴离子复分解获得，与手性对映体纯阴离子P（o-C6 Cl 4 O2）3-（（Δ）-TRISPHAT-; 81%）的盐一样。[（η_5-C_5H_5）Ru（CO）（NCCH_3）_2]+ PF_6 ~-与GBI反应也得到2+ PF_6 ~-（81%）。由（η 5-C5 Me 5）Ru（PPh 3）2（Cl）、GBI和CO随后（对于后三种）通过阴离子复分解制备五甲基吡啶类似物[（η5-C5 Me 5）Ru（CO）（GBI）]+X-（3+X-; X- = Cl-、BF 4-、PF 6-、BAr f-; 61-84%）。用（η_5-C_9H_7）Ru（PPh_3）_2（Cl）和GBI合成了茚基配合物[（η_5-C_9H_7）Ru（PPh_3）（GBI）]+Cl ~-（96%）。配合物的结构均经核磁共振（1H，13 C，31 P，19 F，11 B）和二维光谱表征。
The reaction of 2-guanidinobenzimidazole (GBI) and (η5-C5H5)Ru(PPh3)2(Cl) in refluxing toluene gives the chelate [(η5-C5H5)Ru(PPh3)(GBI)]+Cl– (1+Cl–; 96%). Subsequent anion metatheses yield the BF4–, PF6–, and BArf– (B(3,5-C6H3(CF3)2)4–) salts (77–85%). Reactions with CO give the carbonyl complexes [(η5-C5H5)Ru(CO)(GBI)]+X– (2+X–; X– = Cl–, BF4–, PF6–, BArf–; 87–92%). The last three salts can also be obtained by anion metatheses of 2+Cl– (77–87%), as can one with the chiral enantiopure anion P(o-C6Cl4O2)3– ((Δ)-TRISPHAT–; 81%). The reaction of [(η5-C5H5)Ru(CO)(NCCH3)2]+PF6– and GBI also gives 2+PF6– (81%). The pentamethylcyclopentadienyl analogues [(η5-C5Me5)Ru(CO)(GBI)]+X– (3+X–; X– = Cl–, BF4–, PF6–, BArf–; 61–84%) are prepared from (η5-C5Me5)Ru(PPh3)2(Cl), GBI, and CO followed (for the last three) by anion metatheses. An indenyl complex [(η5-C9H7)Ru(PPh3)(GBI)]+Cl– (96%) is prepared from (η5-C9H7)Ru(PPh3)2(Cl) and GBI. All complexes are characterized by NMR (1H, 13C, 31P, 19F, 11B), with 2D spectra aid...
影响因子：
1.8
作者：
Rodriguez,AndrewA;Yoo,Hoseong;Ziller,JosephW;Shea,KennethJ
通讯作者：
Shea,KennethJ