高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (6): 1062.

• 研究论文 • 上一篇    下一篇

有机锡修饰的双吡唑甲烷及其与W(CO)5THF的反应

赵书斌, 文振康, 王积涛, 唐良富   

  1. 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:2004-06-01 出版日期:2005-06-10 发布日期:2005-06-10
  • 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:lftang@nankai.edu.cn E-mail:lftang@nankai.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:20172029)资助.

Modification of Bis(pyrazol-1-yl)methanes with Organotin and Their Reactions with W(CO)5THF

ZHAO Shu-Bin, WEN Zhen-Kang, WANG Ji-Tao, TANG Liang-Fu   

  1. State Key Laboratory of Elemento-Organic Chemistry, Department of Chemistry, Nankai University, Tianjin 300071, China
  • Received:2004-06-01 Online:2005-06-10 Published:2005-06-10

摘要: 通过双吡唑甲基锂(LiCHPz2)与有机锡卤化物(R3SnX)的反应合成了一系列有机锡修饰的双吡唑甲烷配体(R3SnCHPz2).由于锡上取代基的不同,这些配体与W(CO)5THF反应时表现出了不同的反应方式.三芳基锡修饰的双吡唑甲烷与W(CO)5THF反应发生Sn—C(sp3)键对W(0)中心的氧化加成;而三苄基锡修饰的双吡唑甲烷与其反应时仅给出羰基取代产物[Bz3SnCHPz2W(CO)4].另外,二苯基苄基锡以及三(2-苯基-2-甲基丙基)锡修饰的双吡唑甲烷配体类似的反应导致配体的分解,产生单吡唑配体取代的羰基钨衍生物[W(CO)5PzH]以及脱有机锡的双吡唑甲烷四羰基钨衍生物[CH2Pz2W(CO)4].

关键词: 双吡唑甲烷, 有机锡, 羰基钨

Abstract: The modification of bis(pyrazol-1-yl)methanes by substitution of organotin groups on the methine carbon was carried out by the reaction of bis(pyrazol-1-yl)methyllithium(LiCHPz2) with organotin halide(R3SnX), yielding a series of R3SnCHPz(R=alkyl or aryl; Pz=substituted pyrazole) ligands. Upon the treatment of these ligands with W(CO)5THF, they displayed versatile reactivities, depending on the properties of substitutions on the tin atom. The reaction of Ar3SnCHPz2 with (W(CO)5THF) resulted in the oxidative addition of the tin-carbon(sp3) bond to the tungsten(0) center, while the similar reaction of Bz3SnCHPz2(Bz=benzyl; Pz=3,5-dimethylpyrazole) only gave decarbonylation complex of (Bz3Sn)(CHPz2W(CO)4). In addition, the reactions of Ph2BzSnCHPz2 and (PhMe2CCH2)3SnCHPz2 with (W(CO)5THF) resulted in the partial decomposition of ligands to yield CH2Pz2W(CO)4 and , with the loss of organotin groups.

Key words: Bis(pyrazol-1-yl)methane, Organotin, W(CO)6

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