Flash Communication: Metathesis of Heavy Alkyne Analogues in Solution via Dissociation of m-Terphenyl Substituted Distannynes and Diplumbynes

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-06-10 DOI:10.1021/acs.organomet.5c0007410.1021/acs.organomet.5c00074

Joshua D. Queen*, and , Philip P. Power*,

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引用次数: 0

Abstract

The terphenyl substituted distannynes and diplumbynes ArEEAr (E = Sn, Pb; Ar = Ar^iPr4, C₆H₃-2,6-(C₆H₃-2,6-ⁱPr₂)₂; Ar = Ar^iPr6, C₆H₃-2,6-(C₆H₂-2,4,6-ⁱPr₃)₂) undergo metathesis and ligand redistribution reactions in solution at ambient temperature to yield mixtures of asymmetrically substituted and heterometallic heavy alkyne analogues. The ambient temperature solution EPR spectrum of Ar^iPr6SnSnAr^iPr6 shows a weak signal corresponding to the (SnAr^iPr6)^· radical, and the thermolysis of Ar^iPr8PbPbAr^iPr8 (Ar^iPr8 = C₆H-3,5-ⁱPr₂-2,6-(C₆H₂-2,4,6-ⁱPr₃)₂) in toluene yields the plumbylene Pb(CH₂C₆H₅)Ar^iPr8, also suggesting that a transient Pb(Ar^iPr8)^· radical is liberated on heating. These results provide further evidence to the solution equilibria of the heavy group 14 analogues with the respective one-coordinate metal radicals.

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闪光通讯：通过间terphenyl取代的Distannynes和Diplumbynes的解离，在溶液中重炔类似物的再合成

三苯基取代的二苯乙烯和二铅苯ArEEAr (E = Sn, Pb；Ar = AriPr4, c6h3 -2,6-(c6h3 -2,6- ipr2)2；Ar = AriPr6, C6H3-2,6-(C6H2-2,4,6- ipr3)2)在室温下在溶液中进行复分解和配体重分配反应，生成不对称取代和异金属重炔类似物的混合物。AriPr6SnSnAriPr6的室温溶液EPR谱显示出与（SnAriPr6）·自由基对应的弱信号，AriPr8PbPbAriPr8 （AriPr8 = c6h -3,5- ipr2 -2,6-(c6h2 -2,4,6- ipr3)2）在甲苯中热裂解生成铅烯Pb(CH2C6H5)AriPr8，也表明在加热时释放了一个瞬时Pb（AriPr8）·自由基。这些结果进一步证明了重基团14类似物与相应的单坐标金属自由基的溶液平衡。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.