Isolation and Reactivity of Homoleptic Diphosphene Lead Complexes

Ming Chen; Zhaoyin Zhang; Jun Liu; Gongyu Li; Lili Zhao; Zhenbo Mo

doi:10.1002/anie.202312837

Isolation and Reactivity of Homoleptic Diphosphene Lead Complexes

Angew Chem Int Ed Engl. 2023 Nov 27;62(48):e202312837. doi: 10.1002/anie.202312837. Epub 2023 Oct 27.

Authors

Ming Chen¹, Zhaoyin Zhang², Jun Liu³, Gongyu Li³, Lili Zhao², Zhenbo Mo¹

Affiliations

¹ State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin, 300071, China.
² Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing, 211816, China.
³ State Key Laboratory of Medicinal Chemical Biology, Tianjin Key Laboratory of Biosensing and Molecular Recognition, Research Center for Analytical Science, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin, 300071, China.

PMID: 37837247
DOI: 10.1002/anie.202312837

Abstract

Due to their limited capacity for π-backdonation, isolation of π-complexes of main-group elements remains a great challenge. We report herein the synthesis of a homoleptic diphosphene lead complex (2) from the degradation of P₄ with a bis(germylene)-stabilized Pb(0) complex. Structural and computational studies showed that 2 possesses significant π bonding interactions between Pb atom and diphosphene ligands, which is reminiscent of transition-metal diphosphene complexes. Consistent with its unique electronic structure, complex 2 can deliver Pb(0) atoms to perform redox reaction with an iminoquinone to produce a cyclic plumbylene (4) and perform 2,5-dimethyl-3,4-dimethylimidazol-1-ylidene (IMe₂ Me₂ ) induced phosphorus cation abstraction to give an anionic PbP₃ complex (6).

Keywords: Carboranes; Diphosphene; P4 Activation; Plumbylone; π-Complex.

Abstract

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