Reactions of μ-Ethynediyl Complexes of Transition Metals: Selective Double Insertion of Isocyanides and Molecular Structure of CC(=NPh)C(=NPh)Pd(PEt3)2Cl>

DOI: 10.1039/DT9910001531

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Journal of the Chemical Society, Dalton Transactions p. 1531 - 1536 (1991)

Update date:2022-08-02

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Authors:

Onitsuka, Kiyotaka

Ogawa, Hiroo

Joh, Takashi

Takahashi, Shigetoshi

Yamamoto, Yasuhiro

Yamazaki, Hiroshi

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Article abstract of DOI:10.1039/DT9910001531

The μ-ethynediyl-dipalladium complexes CPd(PR3)2X> 1 (X=Cl or I, R=Et or Bu) react with aryl isocyanides R'NC (R'=Ph, 4-NO2C6H4, or 2,6-Me2C6H3) to give double-insertion products C(=NR')C(=NR')Pd(PR3)2X> 2, selectively.Complexes 2 have been characterized by IR, mass, 1H, 13C-<1H>, and 31P-<1H> NMR spectra.Selective double insertion is peculiar to the μ-ethynediyl dinuclear complexes, and other dipalladium complexes CYC<*>Pd(PR3)2Cl> (Y= bond or C6H4) and mononuclear acetylide complexes CR)> (R=Ph or 4-MeOC6H4) give normal single-insertion products, respectively.The dicationic complex <(PhNC)(Et3P)2PdC<*>CPd(PEt3)2(CNPh)>2 has been isolated as an intermediate, which reacts with NR4X (R=Et or C5H11; X=Cl, Br or I) to give double-insertion products 2.The structure of C(=NPh)C(=NPh)Pd(PEt3)2Cl> has been determined by X-ray analysis: space group P2₁/c, a=11.488(3), b=24.997(5), c=18.659(4) Angstroem, β=112.91(2) deg, and Z=4.

Full text of DOI:10.1039/DT9910001531

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