Dinuclear Triazole-Derived Janus-Type N-Heterocyclic Carbene Complexes of Palladium: Syntheses, Isomerizations, and Catalytic Studies toward Direct C5-Arylation of Imidazoles

被引：41
|
作者：
Guo, Shuai [1 ]
Han Vinh Huynh [1 ]
机构：
[1] Natl Univ Singapore, Dept Chem, Singapore 117543, Singapore
来源：
ORGANOMETALLICS | 2014年 / 33卷 / 08期
关键词：
DIRECT ARYLATION; STRUCTURAL FEATURES; DICARBENE COMPLEXES; LIGANDS; REMOTE; AZOLES; REGIOSELECTIVITY; DIYLIDENE; PHOSPHINE; SOLVENTS;
D O I：
10.1021/om500139b
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The dipalladium triazolidine-diylidene complex all-trans-[PdBr2(CH3CN)](2)(mu-ditz) (1) (ditz = 1,2,4-trimethyltriazolidine-3,5-diylidene) was synthesized via in situ deprotonation of the precursor salt with a basic metal precursor. Ligand replacements of all-trans-1 with monodentate or chelating phosphines afforded the dicarbene-bridged complexes all-cis-[PdBr2-(PPh3)](2)(mu-ditz) (2) and [PdBr(DPPP)](2)(mu-ditz)Br-2 (3), respectively. Bromido substitution of all-cis-2 gave tetra-acetato complex all-cis-[Pd(CH3COO)(2)(PPh3)](2)(mu-ditz) (4) with retention of the configuration as the predominant product. In addition, monopalladium triazolin-5-ylidene complexes trans-[PdBr2(CH3CN)(tazy)] (6, tazy =1,4-dimethyltriazolin-5-ylidene), cis-[PdBr2(PPh3)(tazy)] (7), [PdBr(DPPP)(tazy)]Br (8), and cis-[Pd(CH3COO)(2)(PPh3)(tazy)] (9) were also synthesized as the respective mononuclear equivalents for comparison. A comparative catalytic study revealed the general superiority of dinuclear complexes 1-4 over their respective mononuclear counterparts 6-9 in the direct C5-arylation reaction of 1-methylimidazoles. Overall, mixed dicarbene/diphosphine complex 3 showed the best catalytic performance.
引用
收藏
页码：2004 / 2011
页数：8
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