高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (9): 1715.

• 研究论文 • 上一篇    下一篇

双(3,5-二甲基-4-苄基吡唑)甲烷ⅥB族羰基化合物的合成及反应

王志宏, 唐良富, 杨智, 王积涛   

  1. 南开大学化学系, 天津 300071
  • 收稿日期:2001-05-18 出版日期:2002-09-24 发布日期:2002-09-24
  • 通讯作者: 唐良富(1970年出生),男,博士,副教授,从事金属有机化学研究.E-mail:tanglf@eyou.com. E-mail:tanglf@eyou.com.
  • 基金资助:

    国家自然科学基金(批准号:2017202929902002);高等学校博士学科点专项科研基金资助

Synthesis and Reactivity of Group 6 Metal Carbonyl Complexes Containing Bis(3,5-dimethyl-4-benzylpyrazol-1-yl)methane

WANG Zhi-Hong, TANG Liang-Fu, YANG Zhi, WANG Ji-Tao   

  1. Department of Chemistry, Nankai University, Tianjin 300071, China
  • Received:2001-05-18 Online:2002-09-24 Published:2002-09-24

PDF (PC)

被引次数

6

摘要： 通过3,5-二甲基-4-苄基吡唑与二溴甲烷在相转移催化下反应,合成了一个新的多吡唑烷配体双(3,5-二甲基-4-苄基吡唑)甲烷.该配体与M(CO)6(M=Cr,Mo,W)在光照下反应可以得到双(3,5-二甲基-4-苄基吡唑)甲烷四羰基铬(2)、钼(3)和钨(4).用SnCl4处理化合物3和4可以高产率地制得含Mo(W)—Sn键的杂双金属配合物.用X射线衍射法测定了化合物4与SnCl4反应产物6的晶体结构.结果表明,该晶体属三斜晶系,P1空间群,晶胞参数a=1.0929(9)nm,b=1.282(1)nm,c=1.282(1)nm,α=102.35(1)°,β=108.62(1)°,γ=97.00(1)°,V=1.799(3)nm3,Z=2,最终结构偏离因子R=0.058,wR=0.1015,GOF=0.905.六元金属杂环W—N—N—C—N—N为船式构象,分子中没有氯桥存在.

关键词: 多吡唑烷, B族羰基化合物, 杂双核金属配合物, 晶体结构

Abstract: Bis(3,5-dimethyl-4-benzylpyrazo-1-yl)methane, CH2(3,5-Me2-4-BzPz)2, is synthesized by the reaction of 3,5-dimethyl-4-benzylpyrazole with CH2Br2 under phase transfer catalysis, which reacts with M(CO)6(M=Cr, Mo or W) under UV irradiation at room temperature to yield bis(3,5-dimethyl-4-benzylpyrazo-1-yl)methane tetracarbonyl chromium, molybdenum or tungsten complex, respectively. Treatment of bis(3,5-dimethyl-4-benzylpyrazo-1-yl)methane tetracarbonyl molybdenum or tungsten with SnCl4 gives the Mo(W)—Sn heterobimetallic complexes in good yields. The molecular structure of CH2(3,5-Me2-4-BzPz)2W(Cl)(CO)3(SnCl3) determined by X-ray crystallography shows that the six-membered W—N—N—C—N—N metallacycle is in a boat form, and no chlorine bridge is observed. The compound crystallizes in the triclinic space group P1, with a=1.0929(9) nm, b=1.282(1) nm, c=1.282(1) nm, α=102.35(1)°, β=108.62(1)°, γ=97.00(1)°, V=1.799(3) nm3, Z=2, R=0.058, wR=0.1015.

Key words: Poly(pyrazo-1-yl)alkane, Group 6 metal carbonyl complex, Heterobimetallic complexes, Crystal structure

中图分类号: 

TrendMD: