Bis ortho metalated palladium complexes. New examples and reactivity. The x-ray crystal structure of cis-(2-PhN:NC6H4)2Pd and cis-(2-PhN:NC6H4)(2-Me2NCH2C6H4)Pd

Abstract

Reaction of bis[ (2-(arylazo)aryl)chloropalladium] with 2-lithio-N,N-dimethylbenzylamine yields the "mixed" ortho-metalated cis-[ (2-arylaz0)aryl) (2-((dimethylamino)methyl)phenyl]palladium], together with both bis(2-(arylazo)aryl)palladium and bis(2-((dimethylamino)methyl)phenyl)palladium. The X-ray structures of cis-[ (bis(2-phenylazo)phenyl)palladium] and of cis-[ (2-((dimethylamino)methyl)phenyl)-(2-(phenylazo)phenyl)palladium] have been determined and compared w i t h those of known related molecules.The ((ary1azo)aryl)palladium complexes fail to insert alkenes. Bis(2-((dimethylamino)methyl)phenyl]-palladium is shown to insert both styrene and carbon monoxide, and the efficient insertion of methyl acrylate into bis[(2-((tert-butylimino)methyl)phenyl)chloropalladium] is also described. @-Elimination following insertion leads to the palladium-free product in each case.

Hydridothiazole Rhodium Complexes as a Result of C-H Bond Activation in Iminothiazoles Chelating Ligands

“…[1H] NMR spectrum, in particular the signal from the metal-carbon bonded atom, is consistent with the presence of the cyclometallated ring[24,31,32] the signal Describes Schematic preparation and structural of iminothiazoles (1-20) chelating ligands. Describes schematic diagram for preparation of "hydridothiazole" rhodium complexes.Table 1.…”

“…Coordination of the metal with nitrogen atom in aryl amines results in a favorable geometry for introducing of the metal into neighboring C-H or C-C bond [21,25,26,30]. Rhodium complexes ( Table 1) were synthesized either by mixing and refluxing equimolar amount of the Schiff base with {RhC1(Ph 3 P)} in THF for 0.5h [31], or by boiling a solution of one equivalent of {Rh( -Cl)(COD)} 2 , with two equivalents of prepared Schiff base with four equivalents of phosphine in THF for 1h, as showed in Scheme (2). The 1 H NMR spectrum of each of the new rhodium complexes in CDCl 3 shows a hydride resonance between -11.49 and -13.27 ppm ( Table 3).…”

“…Interestingly, the hydride 1 H NMR spectrum of compound (31) presented in two types of the hydride spectrum which appear at -11.49 ppm and -12.36 ppm. Also, two31 P-spectrum appears at 37.87 ppm and 29.54 ppm with 2J ( 31 P-1 H), 11.0 and 11.0 Hz and 1J ( 103 Rh-1 H) 12.50 Hz and 12.80 Hz with 1J ( 103 Rh-31 P), of 111 Hz and 118 Hz…”

Cyclopalladated azido complexes containing C,N-donor (HC∼N = 2-(2′-thienyl)pyridine, azobenzene, 3,3′-dimethyl azobenzene, N,N′-dimethylbenzylamine, 2-phenylpyridine) ligands: reactivity towards organic unsaturated compounds and catalytic properties

“…5). In contrast, similar treatments with two equivalents of phosphine give the ionic complex [Pd(C,N-L 1 )(P~P)](N 3 ) (18), in which the azido group acts as a counterion. In these reactions, compared with the Clbridged cyclopalladated complexes, the N 3 -bridged analogs are cleaved to the bis(chelated) compounds in lower yields.…”

1-D networks formed by metal⋯sulfur van der Walls contacts: Novel tetrazole–thiolato Pd(II) and Pt(II) complexes

“…In particular, (a-position)-pyridyl-substituted thiophene derivatives exhibit interesting various coordination behaviors as well as electronic or electroluminescent properties [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23].…”