Palladium(II) -cyano-aminothiophenolate (ocap) complexes.

A series of Pd(II) complexes containing -cyano-aminothiophenolate (ocap) ligands have been prepared and their molecular structures elucidated. Hg(II) ocap complexes, [Hg{SCHXN(CN)}] (X = H, Me) (1), react with NaS to afford HgS and Na[ocap] which reacts with K[PdCl] to afford palladium ocap complexes [Pd{SCHXN(CN)}] (2). A second route to these coordination polymers has also been developed from reactions of 2-aminobenzothiazole (abt) complexes, -PdCl(abt) (3), with NaOH.

Synthesis, structure and reactivity with phosphines of Hg(II) -cyano-aminothiophenolate complexes formed C-S bond cleavage and dehydrogenation of 2-aminobenzothiazoles.

Addition of 2-aminobenzothiazole (abt) and substituted derivatives to Hg(OAc) leads to the high yield formation of -cyano-aminothiophenolate (ocap) complexes [Hg{SCHXN(CN)}] (X = H, Me, Cl, Br, NO) resulting from dehydrogenation and C-S bond cleavage. The reaction appears to be unique to Hg(OAc) and with HgCl the product [HgCl(abt)] contains an intact abt ligand, but reacts with acetate to afford the ocap complex [Hg{SCHN(CN)}]. Binding of abt to Hg(II) has previously been probed in molecular structures of [Hg(sac)(abt)L] (L = MeOH, DMSO) and these have been reexamined to understand the perturbation of abt upon coordination.

Synthesis and Structural Characterization of Palladium(II) Mixed-Ligand Complexes of -(Benzothiazol-2-yl)benzamide and 1,2-Bis(diphenylphosphino)ethane.

Three novel palladium(II) mixed-ligand complexes of -(benzothiazol-2-yl)benzamide (HL) and 1,2-bis(diphenylphosphino)ethane (dppe), [Pd(HL)(dppe)]Cl (), [Pd(L)(dppe)]Cl (), and [Pd(L)(dppe)] (), were synthesized and fully characterized using Fourier transform infrared, H, C, and P NMR, and molar conductivity measurements. Complex was characterized by single-crystal X-ray diffraction. The ligand HL showed three different coordination modes: a neutral bidentate chelate bound through the endocyclic nitrogen and exocyclic oxygen atoms in , a negatively charged L bound as a bidentate chelate through the endocyclic nitrogen and negatively charged exocyclic oxygen atoms in , and a monodentate bound through the negatively charged endocyclic nitrogen atom in .

Formation of ortho-cyano-aminothiophenolate ligands with versatile binding modes via facile carbon-sulfur bond cleavage of 2-aminobenzothiazoles at mercury(II) centres.

Addition of 2-aminobenzothiazole and substituted derivatives to mercuric acetate in warm ethanol leads to the high yield formation of [Hg{SC6H3XN(C[triple bond, length as m-dash]N)}]n resulting from loss of hydrogen and sulfur-carbon bond cleavage. Addition of phosphines affords a series of complexes in which the new ortho-cyano-aminothiophenolate ligands adopt three different binding modes.