Photochemical C(sp)–C(sp2) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes LnM–C≡P,Journal of the American Chemical Society

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Photochemical C(sp)–C(sp2) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes LnM–C≡P
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-11-10 , DOI: 10.1021/jacs.1c07370
Tim Görlich ₁ , Daniel S Frost ₁ , Nico Boback ₁ , Nathan T Coles ₁ , Birger Dittrich ₂ , Peter Müller ₃ , William D Jones ₄ , Christian Müller ₁

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The photochemical activation of the C(sp)–C(sp²) bond in Pt(0)-η²-aryl-phosphaalkyne complexes leads selectively to coordination compounds of the type L_nPt(aryl)(C≡P). The oxidative addition reaction is a novel, clean, and atom-economic route for the synthesis of reactive terminal Pt(II)-cyaphido complexes, which can undergo [3 + 2] cycloaddition reactions with organic azides, yielding the corresponding Pt(II)-triazaphospholato complexes. The C–C bond cleavage reaction is thermodynamically uphill. Upon heating, the reverse and quantitative reductive elimination toward the Pt(0)-phosphaalkyne-π-complex is observed.

中文翻译：

磷酸炔烃中的光化学 C(sp)–C(sp2) 键活化：反应性末端氰基配合物 LnM–C≡P 的新途径

^{Pt(0)-η 2 -芳基-磷炔配合物中C(}sp )-C( sp ² ) 键的光化学活化选择性地产生L _n Pt(芳基)(C≡P) 类型的配位化合物。氧化加成反应是合成反应性末端 Pt(II)-cyaphido 配合物的一种新颖、清洁和原子经济的途径，它可以与有机叠氮化物进行 [3 + 2] 环加成反应，产生相应的 Pt(II) -三氮杂磷酸盐络合物。C-C 键断裂反应是热力学上坡的。加热后，观察到 Pt(0)-磷炔-π-配合物的反向和定量还原消除。

更新日期：2021-11-24

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