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桥头碳上氮杂芳基功能化的双吡唑甲烷与羰基钨反应
引用本文:丁可,孙遵明,李厚谦,唐良富.桥头碳上氮杂芳基功能化的双吡唑甲烷与羰基钨反应[J].无机化学学报,2013,29(18).
作者姓名:丁可  孙遵明  李厚谦  唐良富
作者单位:南开大学化学系, 元素有机化学国家重点实验室, 天津 300071;南开大学化学系, 元素有机化学国家重点实验室, 天津 300071;南开大学化学系, 元素有机化学国家重点实验室, 天津 300071;南开大学化学系, 元素有机化学国家重点实验室, 天津 300071
基金项目:国家自然科学基金(No.21372124)和NFFTBS(No.J1103306)资助项目
摘    要:研究了(氮甲基咪唑-2-基)双(3,5-二甲基吡唑)甲烷(L1),2-吡啶基双(3,5-二甲基吡唑)甲烷(L2)及4-吡啶基双(3,5-二甲基吡唑)甲烷(L3)与羰基钨的反应,合成了一系列以单齿,双齿及三齿氮配位的羰基金属衍生物LW(CO)5 (L=L1或L3),LW(CO)4 (L=L1,L2或L3)和LW(CO)3 (L=L1或L2).核磁,红外及X-射线单晶衍射分析表明这3种配体表现出了可变的配位方式.在LW(CO)5中,当配体为L1时,其倾向于通过咪唑氮与金属配位,而为L3则倾向于利用吡啶氮与金属作用;在LW(CO)4中,配体L1表现为通过咪唑氮和吡唑氮原子配位的N,N']双齿配体,而L2和L3表现为通过吡唑氮原子配位的N,N]双齿配体;在LW(CO)3中,L1和L2起着N,N,N']三齿螯合配体的作用.

关 键 词:氮配体  双吡唑甲烷  咪唑  吡啶  

Reaction of Tungsten Carbonyl with Bis(pyrazol-1-yl)methanes Functionalized by Azaaryl Groups
DING Ke,SUN Zun-Ming,LI Hou-Qian and TANG Liang-Fu.Reaction of Tungsten Carbonyl with Bis(pyrazol-1-yl)methanes Functionalized by Azaaryl Groups[J].Chinese Journal of Inorganic Chemistry,2013,29(18).
Authors:DING Ke  SUN Zun-Ming  LI Hou-Qian and TANG Liang-Fu
Institution:Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China;Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China;Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China;Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
Abstract:Reaction of W(CO)6 with (N-methylimidazol-2-yl)bis(3,5-dimethylpyrazol-1-yl)methane (L1), (pyridin-2-yl)bis(3,5-dimethylpyrazol-1-yl)methane (L2) and (pyridin-4-yl)bis(3,5-dimethylpyrazol-1-yl)methane (L3) yielded complexes LW(CO)5 (L=L1 or L3), LW(CO)4 (L=L1, L2 or L3) and LW(CO)3 (L=L1 or L2), respectively. NMR, IR and X-ray structural analyses indicated that these three ligands possessed variable coordination modes in these complexes. L1 and L3 acted as monodentate ligands through the imidazolyl nitrogen or the pyridyl nitrogen in LW(CO)5. A N,N'-chelating bidentate ligand through the imidazolyl nitrogen and one pyrazolyl nitrogen was observed in L1W(CO)4, while L2 and L3 acted as N,N-chelating bidentate ligands through two pyrazolyl nitrogens in L2W(CO)4 and L3W(CO)4. A tridentate N,N,N'-chelating ligand through two pyrazolyl nitrogens and the imidazolyl or 2-pyridyl nitrogen was observed in L1W(CO)3 and L2W(CO)3. The different donor ability of these imidazolyl, pyridyl and pyrazolyl nitrogens possibly plays important roles for the structural diversity. CCDC: 1030402, 2; 1030403, 4; 1030404, 7.
Keywords:N ligand  bis(pyrazol-1-yl)methane  imidazole  pyridine  tungsten
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