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15N NMR studies on cyclopalladated Schiff's base complexes

✍ Scribed by P. S. Pregosin; R. Rüedi; C. Anklin

Publisher
John Wiley and Sons
Year
1986
Tongue
English
Weight
449 KB
Volume
24
Category
Article
ISSN
0749-1581

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✦ Synopsis

N NMR spectra for a series of cyclopalladated m-and p-substituted benzylidene Schiffs base complexes have been measured. The dominant factor aEecting the nitrogen chemical shift is the ligand in the trans position to the coordinated nitrogen, and not the aryl ring substituent. Tertiary phosphme ligands trans to the "N=CH moiety weaken the Pd-N bond more than oxygen, chlorine or nitrogen donors, thereby reducing the coordination chemical shift. The values for 6("N) in the free and complexed ligands correlate linearly with one another. 'H and 15N spectra of the geometric isomers [Pd(2a)Cl(pyridine)] and [Pd(2a)C1(NHEt2], where 2a = the 2'-cyclopalladated SchiBps base (5'-OCH,C6H,)CH=N(4-CH,C6H,), were assigned based on the local anisotropic effects of the C1 and nitrogen ligand. For the pyridine complex the assignment is supported by difference NOE, NOESY and COSY measurements.

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