Bridge-splitting reactions and far-infrared spectra of diene derivatives of palladium(II) and platinum(II) complexes
- 1 January 1968
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc. A
- p. 2869-2873
- https://doi.org/10.1039/j19680002869
Abstract
Bridge-splitting reactions of complexes of the type [M(diene·OCH3)X]2(M = PdII, PtII; diene = cyclo-octa-1,5-diene, dicyclopentadiene; X = Cl, Br) by neutral ligands (L) having nitrogen or phosphorus as donor atoms are reported. For the products [M(diene·OCH3)LX] two structures are possble, i.e., with L cis to the olefinic double bond (A) or trans to it (B). On the basis of far-i.r. spectra, structure (A) has been attributed to [Pd(diene·OCH3)(py)Cl] and [Pt(diene·OCH3)LX](L = pyridine and p-toluidine). Structure (B) has been attributed to [Pt(diene·OCH3)(PPh3)X] and to the analogous palladium(II) complexes. From [M(diene·OCH3)(py)Cl] the pyridine is displaced by another neutral ligand, whereas the chloride ion is displaced only by an anionic one. The far-i.r. spectra (500–60 cm.–1) of the dimers [M(diene·OCH3)X]2 are reported and the metal–bridging halogen stretching frequencies are assigned on the basis of a Ci point-group symmetry. ν(M–Clbridging) falls in the range 298–216 cm.–1, ν(M–Brbridging) 201–148 cm.–1, and ν(M–Ibridging) 165–122 cm.–1.Keywords
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