Reactivity towards some weak protic electrophiles of the di-mu-hydroxo complex [{Pd(mu-OH)(tmeda)}(2)][BPh4](2): crystal structure of [{Pd(tmeda)}(2)(mu-OH)(mu-HNC6H4Cl-p)][BPh4](2)

The hydroxo complex [{Pd(mu-OH)(tmeda)}(2)][BPh4](2) (tmeda = N,N,N',N'-tet ramethylethylenediamine) reacts with a wide variety of weak protic electrop hiles H(LL) in a 1:2 molar ratio to give the mononuclear cationic palladium (II) derivatives with the general formula of [Pd(LL)(tmeda)][BPh4] (LL=acet ylacetonate (acac) (1); salicylaldehydate (sal) (2); salicylaldiminate (o-R N=CHC6H4O: R = CH(CH3)(2), (3), C6H5 (4), p-ClC6H4 (5), p-BrC6H4 (6), p-MeC 6H4 (7)); 2-pyrrole-carbaldehydate (pcal) (8); 2-pyridine-methoxo(OCH2-py) (9); picolinate (pic) (10); 8-hydroxyquinolinate (oxin) (11) or the dinucle ar complexes [{Pd(mu-pz)(tmeda)}(2)][BPh4](2) (12) and [{Pd (tmeda)}(2)(mu- OH)(mu-HNC6H4R-p)][BPh4](2) (R = 11 (13), Cl (14) or Me (15)) when reacting with pyrazole or anilines in the same molar ratio. In a related reaction, deprotonation of secondary amines by the hydroxo complex in the presence of carbon disulfide leads to the corresponding dithiocarbamate complexes [Pd( S2CNR2(tmeda)][BPh4] R = Me (16), Et (17) C5H10 (18). The new compounds hav e been characterized by partial elemental analyses, conductance measurement s and spectroscopic (IR, H-1 and C-13 NMR) methods. The crystal structure o f compound 14 has been determined by X-ray diffraction analysis. (C) 1999 E lsevier Science S.A. All rights reserved.