Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
J Am Chem Soc. 2021 May 26;143(20):7635-7640. doi: 10.1021/jacs.1c03333. Epub 2021 May 17.
Dibenzo-7-phosphanorbornadiene-substituted diazene MesNP (, where Mes = mesityl, = anthracene, or CH), a synthetic equivalent of mesitylphosphaazide (MesNP) and anthracene, was synthesized by treatment of [PhBP][Na(OEt)] with [MesN]OTf (OTf = CFSO) in thawing tetrahydrofuran (14% isolated yield). Treatment of with unsaturated molecules cyclooctyne, [Na(dioxane)][OCP] (phosphaethynolate), and Ad-C≡P (Ad = adamantyl) results in the corresponding [3 + 2] phosphaazide-(phospha)alkyne cycloadducts, with concomitant loss of anthracene in 65%, 49%, and 38% isolated yield, respectively. Structural data for the phosphaethynolate cycloadduct ([][Na(12-crown-4)]) were obtained in a single-crystal X-ray diffraction study. A diazatriphosphole was generated by combining with P, a thermally activated anthracene-based molecular precursor to diphosphorus (P). Thermolysis (33-65 °C) of in benzene- leads to anthracene extrusion. This process has a unimolecular kinetic profile and proceeds with activation parameters of Δ = 21.6 ± 0.3 kcal/mol and Δ= -4.9 ± 0.8 cal/(mol K).
二苯并-7-磷杂降冰片二烯取代的重氮杂环庚三烯 MesNP（，其中 Mes = 均三甲苯基， = 蒽，或 CH），是 Mes 膦亚氮（MesNP）和蒽的合成等价物，通过在解冻的四氢呋喃（14%的分离产率）中用[MesN]OTf（OTf = CFSO）处理[PhBP][Na(OEt)]来合成。用不饱和分子环辛炔、[Na(dioxane)][OCP]（磷炔酸盐）和 Ad-C≡P（Ad = 金刚烷基）处理，得到相应的[3 + 2]磷杂氮（磷）炔环加成产物，分别以 65%、49%和 38%的分离产率，同时失去蒽。磷炔酸盐环加成产物([][Na(12-crown-4)])的结构数据是在单晶 X 射线衍射研究中获得的。通过将与 P 结合，生成了一个二氮杂三磷杂环戊烯，P 是一种热激活的基于蒽的二磷前体。在苯中热解（33-65°C）导致蒽的挤出。这个过程具有单分子动力学特征，并且具有 21.6±0.3 kcal/mol 的 Δ 和-4.9±0.8 cal/（mol K）的Δ。
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