Queen Joshua D, Power Philip P
Department of Chemistry, University of California, One Shields Ave., Davis, California 95616, United States.
Organometallics. 2025 Jun 10;44(12):1229-1234. doi: 10.1021/acs.organomet.5c00074. eCollection 2025 Jun 23.
The terphenyl substituted distannynes and diplumbynes ArEEAr (E = Sn, Pb; Ar = Ar, CH-2,6-(CH-2,6-Pr); Ar = Ar, CH-2,6-(CH-2,4,6-Pr)) 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 ArSnSnAr shows a weak signal corresponding to the (SnAr) radical, and the thermolysis of ArPbPbAr (Ar = CH-3,5-Pr-2,6-(CH-2,4,6-Pr)) in toluene yields the plumbylene Pb-(CHCH)-Ar, also suggesting that a transient Pb-(Ar) 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.
三联苯取代的二锡炔和二铅炔ArEEAr（E = Sn，Pb；Ar = Ar，CH-2,6-(CH-2,6-Pr)；Ar = Ar，CH-2,6-(CH-2,4,6-Pr)）在室温下于溶液中发生复分解和配体重新分布反应，生成不对称取代和异金属重炔类似物的混合物。ArSnSnAr的室温溶液电子顺磁共振谱显示出对应于(SnAr)自由基的微弱信号，并且ArPbPbAr（Ar = CH-3,5-Pr-2,6-(CH-2,4,6-Pr)）在甲苯中的热解产生了亚铅烯Pb-(CHCH)-Ar，这也表明加热时会释放出瞬态的Pb-(Ar)自由基。这些结果为第14主族重元素类似物与各自的一配位金属自由基的溶液平衡提供了进一步的证据。
