Synthesis and characterization of new Mannich base ligand. Structure of N, N-bis-(4,5-dimethyl-2-hydroxybenzyl)-N(2-pyridylmethyl)amine

The 10th International Electronic Conference on Synthetic Organic Chemistry session General Organic SynthesisExamples of interesting ligands previously requiring lengthy synthetic procedures have been prepared by one step routes, opening the way to more extensive studies of their complexes and to possible applications. New amine bis-(phenolate) ligand with pendant arm on the amine nitrogen donor have been synthesized, via the Mannich condensation, between a disubstituted phenol, formaldehyde, and N(2-pyridylmethyl)amin

Electronic versus steric control in palladium complexes of carboranyl phosphine-iminophosphorane ligands

[Abstract] A new family of carboranyl phosphine-iminophosphorane ligands was prepared and characterized. The new ligands present a carboranyl group directly attached to the iminophosphorane nitrogen atom through a cage carbon atom (C-carboranyl derivatives L1–L3) or through the B3 boron atom (B-carboranyl derivatives L4 and L5), and the phosphine group on a side chain derived from the diphosphine dppm, i.e. with a two-atom spacer between the P and N donor atoms. The non-carboranyl analogue L6, with a biphenyl group on the nitrogen atom, was also synthesized for comparison. These potential (P, N) ligands were used to obtain palladium complexes (Pd1–Pd6) and, thus, study how the different inductive effect of the carboranyl substituents can modify the coordinating ability of the nitrogen atom. The structural analysis of the complexes revealed two different coordination modes for the ligands: the (P, N) chelate coordination and the unexpected P-terminal coordination, which is not observed for non-carboranyl phosphine-iminophosphoranes. These unexpected structural differences led us to perform DFT calculations on the ligands and metal complexes. The calculations show that the final coordination modes depend on the balance between the electronic and steric properties of the particular carboranyl group.This work was supported by Xunta de Galicia (Spain) (grant no. 10PXIB209285PR)Xunta de Galicia; 10PXIB209285P

Synthesis and Characterization of Homoleptic and Heteroleptic Cobalt, Nickel, Copper, Zinc and Cadmium Compounds with the 2-(Tosylamino)-N-[2-(tosylamino)benzylidene]aniline Ligand

The electrochemical oxidation of anodic metal (cobalt, nickel, copper, zinc and cadmium) in an acetonitrile solution of the Schiff-base ligand 2-(tosylamino)-N-[2-(tosylamino)-benzylidene] aniline (H(2)L) afforded the homoleptic compounds [ML]. The addition of 1,1-diphenylphosphanylmethane (dppm), 2,2`-bipyridine (bipy) or 1,10-phenanthroline (phen) to the electrolytic phase gave the heteroleptic complexes [NiL(dppm)], [ML(bipy)] and [ML(phen)]. The crystal structures of H(2)L (1), [NiL] (2), [CuL] (3), [NiL(dppm)] (4), [CoL(phen)] (5), [CuL(bipy)] (6) and [Zn(Lphen)] (7) were determined by X-ray diffraction. The homoleptic compounds [NiL] and [CuL] are mononuclear with a distorted square planar [MN(3)O] geometry with the Schiff base acting as a dianionic (N(amide)N(amide)N(imine)O(tosyl)) tetradentate ligand. Both compounds exhibit an unusual pi-pi stacking interaction be-tween a six-membered chelate ring containing the metal and a phenylic ring of the ligand. In the heteroleptic complex [NiL(dppm)], the nickel atom is in a distorted tetrahedral [NiN(3)P] environment defined by the imine, two amide nitrogen atoms of the L(2-) dianionic tridentate ligand and one of the phosphorus atoms of the dppm molecule. In the other heteroleptic complexes, [CoL(phen)], [CuL(bipy)] and [ZnL(phen)], the metal atom is in a five-coordinate environment defined by the imine, two amide nitrogen atoms of the dianionic tridentate ligand and the two bipyridine or phenanthroline nitrogen atoms. The compounds were characterized by microanalysis, IR and UV/Vis (Co, Ni and Cu complexes) spectroscopy, FAB mass spectrometry and (1)H NMR ([NiL] and Zn and Cd complexes) and EPR spectroscopy (Cu complexes).Spanish Xunta de Galicia[PGIDIT07PXIB203038PR]Spanish Xunta de GaliciaMinisterio de Ciencia y Tecnologia (MCYT)[CTQ2006-05298BQU]Ministerio de Ciencia y Tecnologia (MCYT