Synthesis and characterization of mono- and dinuclear aryl palladium(II) complexes: oxidative additions of 1,4-dihalogenated benzene or 4,4′-dibromobiphenyl to Pd(PR₃)₄

Hongwei FuState Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, PR China

Qunli SongXuchang Preschool Teachers’ School, Xuchang, PR China

Jing LiState Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, PR China

Zilong ZhangState Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, PR China

Xiao LiState Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, PR China

Hongmei ZhanState Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, PR ChinaCorrespondence[email protected]

Yanxiang ChengState Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, PR ChinaCorrespondence[email protected]

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Pages 482-494 | Received 18 Oct 2013, Accepted 01 Feb 2014, Published online: 14 Mar 2014

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https://doi.org/10.1080/00958972.2014.894993
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Abstract

Mononuclear palladium(II) complexes 1–12, (C₆H₄X-4)PdXʹ(PR₃)₂ (X = I, Br, or Cl; Xʹ = I or Br; R = Ph, Cy, Et, or Me), were synthesized by oxidative addition of 1,4-dihalogenated benzene to Pd(PR₃)₄; dinuclear palladium(II) complexes 13–15, (Me₃P)₂XPd(C₆H₄-1,4)PdXʹ(PMe₃)₂ (X, Xʹ = I or Br), could be obtained only using trimethylphosphine. Another method to prepare 13–15 is via re-oxidative addition of the corresponding mononuclear palladium(II) complexes and Pd(PMe₃)₄. Using 4,4′-dibromobiphenyl as the starting material, the mononuclear palladium(II) complexes [C₆H₄(C₆H₄Br-4)-4]PdBr(PPh₃)₂ (16) and [C₆H₄(C₆H₄Br-4)-4]PdBr(PCy₃)₂ (17) with bulky phosphines could be synthesized at relative low temperature, while dinuclear 18, (Cy₃P)₂BrPd(C₆H₄C₆H₄-4,4ʹ)PdBr(PCy₃)₂, was prepared by bis-oxidative addition at higher temperature. The re-oxidative addition of 16 and Pd(PMe₃)₄ gave dinuclear 19, (Me₃P)₂BrPd(C₆H₄C₆H₄-4,4ʹ)PdBr(PMe₃)₂, accompanying phosphine exchange. X-ray diffraction analysis revealed that formation of dinuclear palladium(II) complexes depends on the reaction temperature, phosphine ligands, and bridging groups.

Graphical Abstract

Keywords:

Aryl palladium(II) complex
Synthesis
Phosphine
Oxidative addition
Crystal structure

Funding

This work is supported by the National Natural Science Foundation of China [grant numbers 21174141 and 51073152].

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