Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands
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- 作者：Allison L. Brazeau ; Mikko M. H盲nninen ; Heikki M. Tuononen ; Nathan D. Jones ; Paul J. Ragogna
- 刊名：The Journal of the American Chemical Society
- 出版年：2012
- 出版时间：March 21, 2012
- 年：2012
- 卷：134
- 期：11
- 页码：5398-5414
- 全文大小：704K
- 年卷期：v.134,no.11(March 21, 2012)
- ISSN：1520-5126
文摘
The reported chemistry and reactivity of guanidinate supported group 15 elements in the +3 oxidation state, particularly phosphorus, is limited when compared to their ubiquity in supporting metallic elements across the periodic table. We have synthesized a series of chlorophosphines utilizing homo- and heteroleptic (dianionic)guanidinates and have completed a comprehensive study of their reactivity. Most notable is the reluctancy of these four-membered rings to form the corresponding N-heterocyclic phosphenium cations, the tendency to chemically and thermally eliminate carbodiimide, and the scarcely observed ring expansion by insertion of a chloro(imino)phosphine into a P鈥揘 bond of the P鈥揘鈥揅鈥揘 framework. Computational analysis has provided corroborating evidence for the unwillingness of the halide abstraction reaction by demonstrating the exceptional electron acceptor properties of the target phosphenium cations and the underscoring strength of the P鈥揦 bond.