Isolable zero-valent Ditin(0) and Diplumbum(0) complexes.

Shen, Jinghang; Zhang, Zhengting; Ke, Xiaokang; Peng, Luming; Zhao, Qianyi; Zhu, Congqing; Zhu, Qin · Nat Commun · 2025

basic_science · Level V

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Abstract

Although complexes with monatomic zero-valent main group centers have been reported, diatomic zero-valent complexes are extremely rare and all previously reported examples were stabilized by either carbene or silylene ligands. Here, we present the isolation of diatomic E(0)-E(0) (E = Sn, Pb) species supported by two [N{CH₂CH₂NP<sup>i</sup>Pr₂}₃Sn] fragments. The reaction of trilithium salt N{CH<sub>2</sub>CH<sub>2</sub>NLiP<sup>i</sup>Pr<sub>2</sub>}<sub>3</sub> with SnCl<sub>2</sub> yields complex [N{CH<sub>2</sub>CH<sub>2</sub>NP<sup>i</sup>Pr<sub>2</sub>}<sub>3</sub>]<sub>2</sub>Sn<sub>3</sub> (1) with a Sn<sub>3</sub> chain. The reduction of the mixture of 1 and SnCl<sub>2</sub> with KC<sub>8</sub> produces the catenated Sn<sub>4</sub> chain [N{CH<sub>2</sub>CH<sub>2</sub>NP<sup>i</sup>Pr<sub>2</sub>}<sub>3</sub>Sn<sub>2</sub>]<sub>2</sub> (2), featuring a diatomic Sn(0)-Sn(0) unit. Further reduction of 2 with KC<sub>8</sub> yields the alkali metal ion-bridged complex [N{CH<sub>2</sub>CH<sub>2</sub>NP<sup>i</sup>Pr<sub>2</sub>}<sub>3</sub>SnK]<sub>2</sub> (3). Moreover, the reaction of 3 with PbI<sub>2</sub> and KC<sub>8</sub> affords [N{CH<sub>2</sub>CH<sub>2</sub>NP<sup>i</sup>Pr<sub>2</sub>}<sub>3</sub>SnPb]<sub>2</sub> (4), which can also be generated by the reaction of KC<sub>8</sub> with PbI<sub>2</sub> and [N{CH<sub>2</sub>CH<sub>2</sub>NP<sup>i</sup>Pr<sub>2</sub>}<sub>3</sub>SnLi]<sub>2</sub> (5). Complex 4 features a diatomic Pb(0)-Pb(0) unit, representing a heavy diatomic zero-valent main group complex. The presence of diatomic E(0)-E(0) (E = Sn, Pb) units in complexes 2 and 4, respectively, is further confirmed by computational studies.