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NMR Spectroscopic Studies of Palladium(II) Complexes of Bidentate Diphenylphosphane Ligands with Acetate and Tosylate Anions: Complex Formation and Structures
Author(s) -
Mooibroek Tiddo J.,
Bouwman Elisabeth,
Lutz Martin,
Spek Anthony L.,
Drent Eite
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900974
Subject(s) - chemistry , denticity , steric effects , ligand (biochemistry) , palladium , nuclear magnetic resonance spectroscopy , crystallography , stereochemistry , crystal structure , organic chemistry , catalysis , receptor , biochemistry
The synthetic pathways towards Pd II complexes of functionalized bidentate diphenylphosphane ligands of the type [Pd(ligand)(anion) 2 ] and [Pd(ligand) 2 ](anion) 2 have been investigated. Eighteen different ligands have been used in combination with strongly (acetate, OAc – ) or weakly (tosylate, OTs – ) coordinating anions. The solid‐state structure of some representative complexes was determined with X‐ray crystallography. It is shown that the solid‐state structures are fully retained in solution. The formation of [Pd(ligand)(anion) 2 ]‐type complexes was studied in detail by 1 H‐ and 31 P‐NMR spectroscopy. Depending on the ligand structure, the complex is formed instantaneously, via a polynuclear intermediate or is not formed at all. Complex formation is demonstrated to depend on the length and rigidity of the ligand backbone and on the steric bulk at the ortho position of the phenyl rings on phosphorus. It was also found that the coordinating ability of the anions can alter the structure of the kinetic and/or thermodynamic product.