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Updated: May 22, 2025
Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Isolable zero-valent Ditin(0) and Diplumbum(0) complexes
Jinghang Shen1, Zhengting Zhang1, Xiaokang Ke1
1State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
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{CH₂CH₂NPiPr₂}₃Sn] fragments. The reaction of trilithium salt N{CH2CH2NLiPiPr2}3 with SnCl2 yields complex [N{CH2CH2NPiPr2}3]2Sn3 (1) with a Sn3 chain. The reduction of the mixture of 1 and SnCl2 with KC8 produces the catenated Sn4 chain [N{CH2CH2NPiPr2}3Sn2]2 (2), featuring a diatomic Sn(0)-Sn(0) unit. Further reduction of 2 with KC8 yields the alkali metal ion-bridged complex [N{CH2CH2NPiPr2}3SnK]2 (3). Moreover, the reaction of 3 with PbI2 and KC8 affords [N{CH2CH2NPiPr2}3SnPb]2 (4), which can also be generated by the reaction of KC8 with PbI2 and [N{CH2CH2NPiPr2}3SnLi]2 (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.
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