化学学报 ›› 2011, Vol. 69 ›› Issue (21): 2567-2573.DOI: 10.6023/A1103311B 上一篇    下一篇

研究论文

含钼(钨)锡键的四元金属有机杂环化合物的合成与反应研究

张晓燕1,宋海滨2,唐良富*,2   

  1. (1东北大学秦皇岛分校材料科学与工程系 秦皇岛 河北 066004)
    (2南开大学化学系 元素有机化学国家重点实验室 天津 300071)
  • 收稿日期:2011-03-31 修回日期:2011-06-23 出版日期:2011-11-14 发布日期:2011-07-12
  • 通讯作者: 唐良富 E-mail:lftang@nankai.edu.cn
  • 基金资助:

    国家自然科学基金

Synthesis and Reactivity of the Four-membered Heterometallacycles with M—Sn (M=Mo or W) Bonds

Zhang Xiaoyan1 Song Haibin2 Tang Liangfu*,2   

  1. (1 Department of Materials Science and Engineering, Northeastern University at Qinhuangdao, Hebei 066004)
    (2 Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071)
  • Received:2011-03-31 Revised:2011-06-23 Online:2011-11-14 Published:2011-07-12

通过三苯基锡基-双(3,5-二甲基吡唑)甲烷与羰基钼的反应合成了钼锡键合的四元金属杂环化合物CH(3,5- Me2Pz)2Mo(CO)3SnPh3 (Pz=1-吡唑基). 当用叔丁基异腈处理该化合物及其钨类似物时, 伴随着有机锡结构单元的丢失, 金属钼(钨)上发生还原消除并分解得到化合物CH2(3,5-Me2Pz)2M(CO)3(CNBu-t) (M为Mo或W). 另外, 该化合物与三苯基膦或亚磷酸甲酯及异丙酯反应时, 只发生羰基取代反应得到化合物CH(3,5-Me2Pz)2Mo(CO)2(PR3)SnPh3 (R为苯基、甲氧基及异丙氧基). 而用亚磷酸苯酯与之反应, 除得到羰基取代产物外, 还伴随着P—O/C键的交换, 得到金属钼上还原消除的产物(PhO)2PCH(3,5-Me2Pz)2Mo(CO)3.

关键词: 双吡唑甲烷, 金属杂环, 第六族金属羰基化合物, 有机锡, 晶体结构

Four-membered heterometallacylic complex CH(3,5-Me2Pz)2Mo(CO)3SnPh3 (Pz=pyrazol-1-yl) has been obtained by the reaction of Ph3SnCH(3,5-Me2Pz)2 with Mo(CO)6. Treatment of this complex and its tungsten analog with CNBu-t resulted in the reductive elimination reaction to give complexes CH2(3,5- Me2Pz)2M(CO)3(CNBu-t) (M=Mo or W) with the loss of organotin fragment. In addition, reaction of this complex with PR3 (R=Ph, OMe or OPr-#em/em#) only yielded complexes CH(3,5-Me2Pz)2Mo(CO)2(PR3)SnPh3. While the similar reaction with P(OPh)3 led to the P—O/C exchange to give the reductive elimination product (PhO)2PCH(3,5-Me2Pz)2Mo(CO)3, besides the substituted reaction of the carbonyl group.

Key words: bis(pyrazol-1-yl)methane, heterometallacycle, group 6 metal carbonyl complex, organotin, crystal structure

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