Nasrullah Ayu Afiqah, Zander Edgar, Dankert Fabian, Petrov Andrey, Surkau Jonas, Baráth Eszter, Hering-Junghans Christian
Leibniz Institut für Katalyse e.V. (LIKAT) A.-Einstein-Str. 29a 18059 Rostock Germany
Pusat Persediaan Sains dan Teknologi, Universiti Malaysia Sabah Jln UMS 88400 Kota Kinabalu Sabah Malaysia.
Chem Sci. 2025 Mar 13;16(16):6909-6917. doi: 10.1039/d4sc07636b. eCollection 2025 Apr 16.
The 1,3-phosphaazaallene TerP = C=NBu (Ter = 2,6-(2,6-iPrCH)-CH) is thermally labile towards iso-butene elimination and formation of the corresponding cyanophosphine TerP(H)CN (1). In previous work we have shown facile deprotonation of 1 with K[N(SiMe) and formation of cyanophosphide [(TerPCN)K]. We now present the alkali metal tethered cyanophosphides [(TerPCN)M(crown)] (M = Na, K; crown = 15-c-5, 18-c-6) and their structural diversity in the solid state depending on the metal (M) and the crown ether. Facile oxidation of [TerPCN][M(crown)] with O yields the formal cyanide adducts of dioxophosphoranes [TerPO(CN)]. Surprisingly, [TerPO(CN)] is obtained as a mixture of the cyanide and isocyanide isomers, indicating a coordination isomerism. This phenomenon is corroborated by experimental and theoretical studies revealing the cyanide isomer to be thermodynamically more stable. The oxidation with elemental sulphur gave the corresponding dithiophosphorane cyanide adduct [TerPS(CN)], in which no isomerism was observed. This points to a crucial role of triplet oxygen in the isomerisation process. Monooxidation occurs when [TerPO(CN)] salts were treated with NO, giving formal anionic phoshinidene monoxide adducts.
1,3 - 磷杂丙二烯TerP = C=NBu（Ter = 2,6 - (2,6 - iPr₂C₆H₃)₂C₆H₃）对异丁烯消除反应以及相应的氰基膦TerP(H)CN（1）的形成具有热不稳定性。在之前的工作中，我们已经证明了1与K[N(SiMe₃)₂]能 facile去质子化并形成氰基磷化物[(TerPCN)K]。我们现在展示了碱金属连接的氰基磷化物[(TerPCN)M(crown)]（M = Na、K；crown = 15 - c - 5、18 - c - 6）及其在固态下取决于金属（M）和冠醚的结构多样性。[TerPCN][M(crown)]与O₂的 facile氧化反应生成了二氧代磷杂环戊烷的形式氰化物加合物[TerPO(CN)]。令人惊讶的是，[TerPO(CN)]是以氰化物和异氰化物异构体的混合物形式获得的，这表明存在配位异构现象。实验和理论研究证实了这种现象，揭示出氰化物异构体在热力学上更稳定。与元素硫的氧化反应生成了相应的二硫代磷杂环戊烷氰化物加合物[TerPS(CN)]，其中未观察到异构现象。这表明三线态氧在异构化过程中起关键作用。当[TerPO(CN)]盐用NO处理时会发生单氧化反应，生成形式上的阴离子磷亚胺单氧化物加合物。
