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

快讯:溶液中重炔烃类似物的复分解反应,通过间三联苯取代的二锡炔和二铅炔的解离实现。

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Abstract

The terphenyl substituted distannynes and diplumbynes ArEEAr (E = Sn, Pb; Ar = Ar(iPr4), C(6)H(3)-2,6-(C(6)H(3)-2,6-(i)Pr(2))(2); Ar = Ar(iPr6), C(6)H(3)-2,6-(C(6)H(2)-2,4,6-(i)Pr(3))(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(iPr6)SnSnAr(iPr6) shows a weak signal corresponding to the (SnAr(iPr6))(·) radical, and the thermolysis of Ar(iPr8)PbPbAr(iPr8) (Ar(iPr8) = C(6)H-3,5-(i)Pr(2)-2,6-(C(6)H(2)-2,4,6-(i)Pr(3))(2)) in toluene yields the plumbylene Pb-(CH(2)C(6)H(5))-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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