Reactivity of phosphaalkyne tBuCP toward a Ga‐functionalized germylene

Xiaofei Sun, Peter Werner Roesky
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Abstract

Phosphaalkynes are the heavier congener of nitriles which feature a polarized Cδ−≡Pδ+ triple bond. Since the isolation of the first phosphaalkyne in 1981, these compounds have become important ligands for transition metals and valuable building blocks in synthetic chemistry. The reported reactivity with germylenes is rare, to expand this chemistry, we studied the reactivity of the recently developed gallium‐substituted germylene 1 ([LPhGe–Ga(Cl)LBDI] (LPh = PhC(NtBu)2; LBDI = [{2,6‐iPr2C6H3NCMe}2CH]) with tBuC≡P. Already at room temperature, insertion of the phosphaalkyne into the Ga–Ge bond occurred, resulting a metal‐functionalized (Z)‐phosphaalkenyl complex [LPhGe{C(tBu)=P}–Ga(Cl)LBDI] (2). Complex 2 was characterized by single crystal X‐ray diffraction analysis and spectroscopic methods (1H, 13C{1H}, 31P{1H} NMR and IR).
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膦炔类 tBuCP 与镓官能化胚芽烯的反应活性
磷炔是腈类化合物中较重的同系物,具有极化的 Cδ-≡Pδ+ 三键。自 1981 年分离出第一种磷炔以来,这些化合物已成为过渡金属的重要配体和合成化学的重要构件。据报道,与锗烯的反应很少见,为了扩展这种化学反应,我们研究了最近开发的镓取代锗烯 1([LPhGe-Ga(Cl)LBDI](LPh = PhC(NtBu)2;LBDI = [{2,6-iPr2C6H3NCMe}2CH])与 tBuC≡P 的反应。在室温下,磷炔就已经插入到了 Ga-Ge 键中,形成了金属官能化的(Z)-磷炔络合物 [LPhGe{C(tBu)=P}-Ga(Cl)LBDI](2)。通过单晶 X 射线衍射分析和光谱方法(1H、13C{1H}、31P{1H} NMR 和 IR)对络合物 2 进行了表征。
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