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- Phosphine-Exchange Induced Intramolecular Substitution Reaction of [{(η[fec3]-C邚H邚)Fe(CO)[feaf]}[feaf](μ-η[fec1]:η[fec1]-PPh [feaf]CH[feaf]CH[feaf]PPh[feaf])[fec7]][PF[feb8][fed2]][feaf]
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題名 | Phosphine-Exchange Induced Intramolecular Substitution Reaction of [{(η[fec3]-C邚H邚)Fe(CO)[feaf]}[feaf](μ-η[fec1]:η[fec1]-PPh [feaf]CH[feaf]CH[feaf]PPh[feaf])[fec7]][PF[feb8][fed2]][feaf]=由膦基交換引發之[{(η[fec3]-C邚H邚)Fe(CO)[feaf]}[feaf](μ-η[fec1]:η[fec1]-PPh [feaf]CH[feaf]CH[feaf]PPh[feaf])[fec7]][PF[feb8][fed2]][feaf]分子內取代反應 |
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作者 | 彭震; 劉陵崗; Peng, James; Liu, Ling-kang; |
期刊 | 中央研究院化學研究所集刊 |
出版日期 | 19980300 |
卷期 | 45 1998.03[民87.03] |
頁次 | 頁27-43 |
分類號 | 346.01 |
語文 | eng |
關鍵詞 | 膦基交換; 分子; 取代反應; |
中文摘要 | 利用低溫下17-19e反應路徑可自2:1(η��-C�NH�N)Fe(CO)�涅/dppe的THF溶液中順 利製備出[{(η��-C�NH�N)Fe(CO)�破��(u-η��:η��-dppe)�ヅ[PF�輊涘�砥C在固態中,陽 離子[{(η��-C�NH�N)Fe(CO)�破��(u-η��:η��-dppe)�ヅ以PF�輊痄Q或BPh�荼痄Q形式存 在時,分子的構型會有差異,前者的兩個Fe中心會在P-C-C-P所鬆散定義的平面同側,後者 Fe-P-C-C-P-Fe則完全反式。1:1[{(η��-C�NH�N)Fe(CO)�破��(u-η��:η��-dppe)�ヅ [PF�輊涘��/dppe的CH�蚓N 溶液中,利用自由基機制行再分配,會形成2當量之 [{(η��-C�NH�N)Fe(CO)��(η��-dppe)�吞 [PF�輊涘,不過後續之分子內CO解離反應將之 全量轉化成為(η��-C�NH�N)Fe(CO)(η��-dppe)�吞 [PF�輊涘。 |
英文摘要 | The preparation of [{(η��-C�NH�N)Fe(CO)�破��(u-η��:η��-dppe)�ヅ [PF�輊涘��,dppe= PPH�浚H�浚H�烈Ph��, was achieved starting from 2:1 (η��-C�NH�N) Fe(CO)�疹/dppe in THF at low temperature employing the 17e-19e pathway. In the solid state the conformations for the [{(η��-C�NH�N)Fe(CO)�破��(u-η��:η�縴ppe)�ヅ dication as PF�輊烞alt and as BPh�荼烞alt are different. In the former the two Fe centers are syn with respect to the loosely defined plane of P-C-C-P skeleton whereas in the latter the Fe-P-C-C-P-Fe skeleton is all trans in conformation. The mixture of 1:1 [{(η��-C�NH�N)Fe(CO)�破��(u-η��:η��-dppe)�ヅ [PF�輊涘�� /dppe in CH�蚓N could be made to redistribute towards 2 equiv [{(η��-C�NH�N)Fe (CO)��(η��- dppe)�吞[PF�輊涘 with the radical mechanism, whereby a second-stage unimolecular CO dissociation follows and results in the quantitative production of (η��-C�NH�N)Fe (CO) (η��-dppe)�吞[PF�輊涘. |
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