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RESEARCH PRODUCT

Reactivity Towards Acidic Protic Ligands of Cyclopalladated Di‐μ‐hydroxo Complexes

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The dinuclear hydroxo complexes [{Pd(μ-OH)(C∧N)}2] [C∧N = 2-(2-pyridyl)phenyl (Phpy) (I), 7,8-benzoquinolyl (Bzq) (II) and 2-(2-oxazolinyl)phenyl (Phox) (III)] react in a 1:2 molar ratio with a wide variety of protic electrophiles H(L∧L) bearing different sets of donor atoms (L∧L = O∧O or O∧N) to give the mononuclear neutral palladium(II) derivatives with the general formula [Pd(L∧L)(C∧N)] [O∧O = salicylaldehydate (sal) (1), acetylacetonate (acac) (2) and benzoylacetonate (bzac) (3); O∧N = N-phenylsalicylaldiminate (N-Phsal) (4), N-p-chlorophenylsalicylaldiminate (N-pClPhsal) (5), 2-pyrrolecarbaldeydate (2-pcal) (6), 8-hydroxyquinolinate (oxin) (7)]. Structural characterisation of complexes I1, I3, I6, II4, II5 and III5 by X-ray diffraction confirmed the proposed formulae. Dinuclear complexes [{Pd(μ-N∧S)(C∧N)}2] [N∧S = 2-pyridinethiolate (spy)] (8) were obtained when treating complexes I–III with 2-mercaptopyridine in the same molar ratio. A related process takes place when the three precursors react with ammonium O,O′-diethyldithiophosphate under mild conditions and complexes [Pd{S(S)P(OEt)2}(C∧N)] (I9–III9) are obtained. Deprotonation of the secondary amine Et2NH by complexes I–III in the presence of carbon disulfideleads to the corresponding dithiocarbamate complexes [Pd(S2CNEt2)(C∧N)] (I10–III10). The new complexes were characterised by analytical and spectroscopic techniques (IR and 1H NMR).(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)