铂类卡宾催化环丙烷化和o-h键插入反应机理的理论分析-theoretical analysis of the mechanism of cyclopropanation and o - h bond insertion catalyzed by platinum carbenes.docxVIP

下载本文档

7
0
约7.51万字
约 65页
2018-05-28 发布于上海
举报
版权申诉

铂类卡宾催化环丙烷化和o-h键插入反应机理的理论分析-theoretical analysis of the mechanism of cyclopropanation and o - h bond insertion catalyzed by platinum carbenes.docx

1、原创力文档（book118）网站文档一经付费（服务费），不意味着购买了该文档的版权，仅供个人/单位学习、研究之用，不得用于商业用途，未经授权，严禁复制、发行、汇编、翻译或者网络传播等，侵权必究。。
2、本站所有内容均由合作方或网友上传，本站不对文档的完整性、权威性及其观点立场正确性做任何保证或承诺！文档内容仅供研究参考，付费前请自行鉴别。如您付费，意味着您自己接受本站规则且自行承担风险，本站不退款、不进行额外附加服务；查看《如何避免下载的几个坑》。如果您已付费下载过本站文档，您可以点击这里二次下载。
3、如文档侵犯商业秘密、侵犯著作权、侵犯人身权等，请点击“版权申诉”（推荐），也可以打举报电话：400-050-0827(电话支持时间：9:00-18:30)。
4、该文档为VIP文档，如果想要下载，成为VIP会员后，下载免费。
5、成为VIP后，下载本文档将扣除1次下载权益。下载后，不支持退款、换文档。如有疑问请联系我们。
6、成为VIP后，您将拥有八大权益，权益包括：VIP文档下载权益、阅读免打扰、文档格式转换、高级专利检索、专属身份标志、高级客服、多端互通、版权登记。
7、VIP文档为合作方或网友上传，每下载1次，网站将根据用户上传文档的质量评分、类型等，对文档贡献者给予高额补贴、流量扶持。如果你也想贡献VIP文档。上传文档

铂类卡宾催化环丙烷化和o-h键插入反应机理的理论分析-theoretical analysis of the mechanism of cyclopropanation and o - h bond insertion catalyzed by platinum carbenes

complex. The results shows the active catalytic species is not a metal-carbene of the type (PH3)2Cl2Pt=CH2 but two carbenoid complexes which can exist in almost two degenerate forms, namely (PH3)2Pt(CH2Cl)Cl (carbenoid A) and (PH3)Pt(CH2PH3)Cl2 (carbenoid B). The reaction proceeds through three pathways: methylene transfer, carbometalation for carbenoid A and the reaction of a monophosphinic species for carbenoid (A and B). The most favored reaction channel is methylene transfer pathway for (PH3)Pt(CH2PH3)Cl2 (carbenoid B) species with a barrier of 31.32kcal/mol in gas phase. The effect ofdichloromethane，THF and benzene solvent are investigated by PCM method. Forcarbenoid A, both methylene transfer and carbometalation pathway barriers to reaction become remarkable lower with the increasing polarity of solvent (from 43.25 and 52.50kcal/mol for no solvent to 25.36 and 38.53kcal/mol in the presence of the dichloromethane). In contrast, the reaction barriers for carbenoid B via the methylene transfer path hoist 6.30kcal/mol while the barriers do not change significantly for the reaction path of a monophosphinic species for carbenoid (A and B).Chapter 4, In this paper we have carried out a theoretical investigation at the DFT (B3LYP) level of the mechanism of the O-H insertion reaction catalyzed by PtCl2 complex. The model system is formed be one allyl alcohol molecule and several diazomethane molecules and the catalyst PtCl2 complex. The resultes indicate that , in breach of traditional view, the starting active catalytic species is not the platinum-carbene Cl2Pt=CH2 or carbenoid ClPtCH2Cl, they should be determined according to the following orders: F-carbenoid T-carbenoid D-carbenoid carbenoid platinum-carbene. On the other hand, the one-step O-H bond insertion reaction has been broved to be a unlikely process, which should consists of three steps: coordination, hydrogen shift, reductive elimination, and the results indicate that the hydrogen