Conformation and ligand exchange reactions of trans-[PdCl(C₆H₄-2-N₂Ph)(PR₃)₂] and related complexes

Anderson, G. K., Cross, R. J., Leaman, S. A., Robertson, F. J., Rycroft, D. S. and Rocamora, M. (1990) Conformation and ligand exchange reactions of trans-[PdCl(C₆H₄-2-N₂Ph)(PR₃)₂] and related complexes. Journal of Organometallic Chemistry, 388(1–2), pp. 221-231. (doi: 10.1016/0022-328X(90)85365-6)

Abstract

Rotation about the metal—carbon bond in trans-[MCl(C₆H₄-2-N₂Ph)(PMe₂Ph)₂] (M = Pd, Pt) is slow at 273 K, and phosphine exchange occurs at ambient temperature. Chloride removal from trans-[PdCl(C₆H₄-2-N₂Ph)L₂] (L = PMe₂Ph, PMe₃, PEt₃) by silver(I) or methyl trifluoromethanesulfonate is complicated by phosphine abstraction, but reaction of [PdCl(C₆H₄-2-N₂Ph-C,N)L] with AgSO₃CF₃ in the presence of 2,6-lutidine (2,6-dimethylpyridine) or 2-fluoropyridine produces [Pd(am)(C₆H₄-2-N₂Ph-C,N)L]SO₃CF₃. Addition of phosphine yields trans-[Pd(am)(C₆H₄-2-N₂Ph)L₂]SO₃CF₃. At or below ambient temperature the 2,6-lutidine complexes exhibit non-equivalent methyl signals in their ¹H NMR spectra, and the 2-fluoropyridine species exist as syn and anti isomers. These observations are consistent with slow rotation about the Pd—C and Pd—N bonds in complexes containing PMe₃ and PEt₃, as well as in those containing PMe₂Ph.

• Item Type: Articles
• Keywords: Organometallic chemistry, NMR spectroscopy.
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Rycroft, Dr David
• Authors: Anderson, G. K., Cross, R. J., Leaman, S. A., Robertson, F. J., Rycroft, D. S., and Rocamora, M.
• Subjects: Q Science > QD Chemistry
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Journal of Organometallic Chemistry
• Publisher: Elsevier
• ISSN: 0022-328X
• ISSN (Online): 1872-8561