Reaction of [P2N2]Ta=CH2(Me) with Ethylene: Synthesis of [P2N2]Ta(C2H4)Et, a Neutral Species with a 
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- 作者：Michael D. Fryzuk ; Samuel A. Johnson ; and Steven J. Rettig
- 刊名：Journal of the American Chemical Society
- 出版年：2001
- 出版时间：February 28, 2001
- 年：2001
- 卷：123
- 期：8
- 页码：1602 - 1612
- 全文大小：164K
- 年卷期：v.123,no.8(February 28, 2001)
- ISSN：1520-5126
文摘
The photolysis of [P2N2]TaMe3 ([P2N2] = PhP(CH2SiMe2NSiMe2CH2)2PPh) produces [P2N2]Ta=CH2(Me) as the major product. The thermally unstable methylidene complex decomposes in solutionin the absence of trapping agents to unidentified products. However, in the presence of ethylene [P2N2]Ta=CH2(Me) is slowly converted to [P2N2]Ta(C2H4)Et, with [P2N2]Ta(C2H4)Me observed as a minor product. Amechanistic study suggests that the formation of [P2N2]Ta(C2H4)Et results from the trapping of [P2N2]TaEt,formed by the migratory insertion of the methylene moiety into the tantalum-methyl bond. The minor product,[P2N2]Ta(C2H4)Me, forms from the decomposition of a tantalacyclobutane resulting from the addition of ethyleneto [P2N2]Ta=CH2(Me) and is accompanied by the production of an equivalent of propylene. Pure [P2N2]Ta(C2H4)Et can be synthesized by hydrogenation of [P2N2]TaMe3 in the presence of PMe3, followed by thereaction of ethylene with the resulting trihydride. Crystallographic and NMR data indicate the presence of a
-agostic interaction between the ethyl group and tantalum center in [P2N2]Ta(C2H4)Et. Partially deuteratedanalogues of [P2N2]Ta(C2H4)Et show a large isotopic perturbation of resonance for both the -protons and the
-protons of the ethyl group, indicative of an equilibrium between a -agostic and an -agostic interaction forthe ethyl group in solution. An EXSY spectrum demonstrates that an additional fluxional process occurs thatexchanges all of the 1H environments of the ethyl and ethylene ligands. The mechanism of this exchange isbelieved to involve the direct transfer of the -agostic hydrogen atom from the ethyl group to the ethyleneligand, via the so-called -hydrogen transfer process.
-agostic interaction between the ethyl group and tantalum center in [P2N2]Ta(C2H4)Et. Partially deuteratedanalogues of [P2N2]Ta(C2H4)Et show a large isotopic perturbation of resonance for both the -protons and the-protons of the ethyl group, indicative of an equilibrium between a -agostic and an -agostic interaction forthe ethyl group in solution. An EXSY spectrum demonstrates that an additional fluxional process occurs thatexchanges all of the 1H environments of the ethyl and ethylene ligands. The mechanism of this exchange isbelieved to involve the direct transfer of the -agostic hydrogen atom from the ethyl group to the ethyleneligand, via the so-called -hydrogen transfer process.