Photochemical Preparation of the cis Isomers of Dichlorobis(tri-n-alkyl-phosphine)palladium(II) (alkyl = Et, Prn, or Bun); the Crystal-structure Analysis of the Overcrowded n-Propyl Homologue

Article abstract of DOI:10.1039/DT9810000635

Ultraviolet irradiation of the trans forms of the title compounds in nitromethane gives up to 70percent of the labile cis isomers, which can be isolated in crystalline form.Irradiation of a 1:1 mixture of trans- and trans-n3)2Cl2> gives almost entirely a 1:1 mixture of the corresponding cis isomers and only a few percent of cis-n3)Cl2>, indicating a predominantly intramolecular mechanism.Crystals of cis-n3)2Cl2> are monoclinic, with space group P2₁/m, a=9.729(1), b=13.816(3), c=9.614(1) Angstroem, β=100.77(1) deg, and Z=2.The structure has been refined to R=0.029 for 1 873 reflections collected by a four-circle diffractometer.The cis-planar structure reveals considerable overcrowding .The Pd-P distances are short (mean 2.322 Angstroem) and the Pd-Cl distances long (mean 2.407 Angstroem), attributable to the trans effect.

Full text of DOI:10.1039/DT9810000635

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