Phospha Derivatives of Tris(2-aminoethyl)amine (tren) and Tris(3-aminopropyl)amine (trpn): Synthesis and Complexation Studies with Group 4 Metals
Phospha Derivatives of Tris(2-aminoethyl)amine (tren) and Tris(3-aminopropyl)amine (trpn): Synthesis and Complexation Studies with Group 4 Metals
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DOI：
10.1021/acs.organomet.5b00065
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发表时间：
2015-03
期刊：
影响因子：
2.8
通讯作者：
M. Sietzen;Sonja Batke;Lukas S. Merz;H. Wadepohl;J. Ballmann
中科院分区：
文献类型：
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作者：
M. Sietzen;Sonja Batke;Lukas S. Merz;H. Wadepohl;J. Ballmann
除了母体磷-trpn外，还合成了三（2-氨基乙基）膦的N，N '，N″-三苯基取代衍生物（ph3 -磷-tren， P(CH2CH2NHR)3, R = Ph）和相关的三（3-氨基丙基）膦的四个衍生物（磷酸-trpn， P(CH2CH2CH2NHR)3, R = iPr, tBu, SitBuMe2, Ph）。在这些配体体系中，发现只有N，N '，N″-三苯基取代磷酸三萜衍生物P(CH2CH2CH2NHPh)3适合与4族金属配位。对于钛、锆和铪，制备了c3对称的内p构型二甲基胺配合物Ph[PN3]M(NMe2)，并将其转化为相应的三酸盐Ph[PN3]M（OTf）。从这些三酸盐开始，通过与Bn2Mg(THF)2反应，得到了苯配合物Ph[PN3]M(Bn) （M = Ti, Zr, Hf）。以钛为例，苯基物质Ph[PN3]Ti（Bn）容易被甲苯热消除，从而形成环金属化物质。这些发现是在上下文中讨论的。
The N,N′,N″-triphenyl-substituted derivative of tris(2-aminoethyl)phosphine (Ph3-phospha-tren, P(CH2CH2NHR)3, R = Ph) and four derivatives of the related tris(3-aminopropyl)phosphine (phospha-trpn, P(CH2CH2CH2NHR)3, R = iPr, tBu, SitBuMe2, Ph) have been synthesized in addition to the parent phospha-trpn. Out of these ligand systems, only the N,N′,N″-triphenyl-substituted phospha-trpn derivative P(CH2CH2CH2NHPh)3 was found to be suitable for coordination to group 4 metals. For titanium, zirconium, and hafnium, the C3-symmetric endo-P-configured dimethylamido complexes Ph[PN3]M(NMe2) of the former ligand have been prepared and converted into the corresponding triflates Ph[PN3]M(OTf). Starting from these triflates, the benzyl complexes Ph[PN3]M(Bn) (M = Ti, Zr, Hf) have been obtained via reaction with Bn2Mg(THF)2. In case of titanium, the benzyl species Ph[PN3]Ti(Bn) is prone to thermal elimination of toluene, which results in the formation of a cyclometalated species. These findings are discussed in context...