Structural correlations for ¹H, ¹³C and ¹⁵N NMR coordination shifts in Au(III), Pd(II) and Pt(II) chloride complexes with lutidines and collidine

Abstract

(1)H, (13)C and (15)N NMR studies of gold(III), palladium(II) and platinum(II) chloride complexes with dimethylpyridines (lutidines: 2,3-lutidine, 2,3lut; 2,4-lutidine, 2,4lut; 3,5-lutidine, 3,5lut; 2,6-lutidine, 2,6lut) and 2,4,6-trimethylpyridine (2,4,6-collidine, 2,4,6col) having general formulae [AuLCl(3)], trans-[PdL(2)Cl(2)] and trans-/cis-[PtL(2)Cl(2)] were performed and the respective chemical shifts (delta(1H), delta(13C), delta(15N)) reported. The deshielding of protons and carbons, as well as the shielding of nitrogens was observed. The (1)H, (13)C and (15)N NMR coordination shifts (Delta(1H) (coord), Delta(13C) (coord), Delta(15N) (coord); Delta(coord) = delta(complex) - delta(ligand)) were discussed in relation to some structural features of the title complexes, such as the type of the central atom [Au(III), Pd(II), Pt(II)], geometry (trans- or cis-), metal-nitrogen bond lengths and the position of both methyl groups in the pyridine ring system.

Efficient microwave-assisted synthesis and characterization of key ruthenium(II) polypyridyl complexes [Ru(bpy)3](PF6)2, [Ru(phen)3](PF6)2, [Ru(bpy)2(phen)](PF6)2 and [Ru(phen)2(bpy)](PF6)2

“…The solid was dissolved in acetonitrile, which was removed under reduced pressure to give [Ru(phen) 3 ](PF 6 ) 2 as a red solid (84 mg, 0.078 mmol, 94%). The 1 H and 13 C{ 1 H} NMR data matched that reported [15]. 1 …”

“…Figure 1. numbering schemes adopted for bpy (a and a′) and phen (B and B′), and the numbering scheme in the literature for phen [15,17]. Dichlorotetrakis(dimethylsulfoxide)ruthenium(II) (40 mg, 0.083 mmol) and 1,10-phenanthroline monohydrate (50 mg, 0.26 mmol, 3.1 equiv) were dissolved in ethylene glycol (6 mL) and heated in a microwave reactor at 160 °C for 15 min.…”

Structural and spectroscopic studies of Au(III) and Pd(II) chloride complexes and organometallics with 2-benzylpyridine

“…10 ppm weaker for [Au(2bzpy)Cl 3 ] than trans-[Pd(2bzpy) 2 Cl 2 ]. The same dependency was reported for many other [AuLCl 3 ] and trans-[PdL 2 Cl 2 ] complexes with N(1)-monodentately bonded azines (L = pyridine; 2-, 3-and 4-methylpyridine; 2,3-, 2,4-, 3,5-and 2,6-dimethylpyridine; 2,4,6-trimethylpyridine; 2-, 3-and 4-phenylpyridine [21,41,42,59,60]). …”

“…(trans-[Pd(2bzpy) 2 Br 2 ][2]), as well as many other trans-[PdL 2 Cl 2 ] complexes with 2-alkyl-or 2-arylpyridines (L = 2-methylpyridine[41], 2,3-dimethylpyridine and 2,4-dimethylpyridine[42], 2-(2-chloroethyl)pyridine[43], 2-(1-methylbenzyl)pyridine[44]). We denote as A and B the species with the H(6) signal at the higher and the lower chemical shift, respectively (d H6(A) > d H6(B) ); the order of other proton peaks may be different (e.g.…”

Applications of nuclear shielding

“…299 1 H, 13 C and 15 N NMR studies of gold(III), palladium(II) and platinum(II) chloride complexes with dimethylpyridines (lutidines: 2,3-lutidine, 2,3lut; 2,4-lutidine, 2,4lut; 3,5-lutidine, 3,5lut; 2,6-lutidine, 2,6lut) and 2,4,6-trimethylpyridine (2,4,6-collidine, 2,4,6col) having general formulas [AuLCl 3 ], trans-[PdL 2 Cl 2 ] and trans-/cis-[PtL 2 Cl 2 ] were performed and the respective chemical shifts (d 1H , d 13C , d 15N ) were reported. 300 The experimental 13 C NMR chemical shift components of uracil in the solid state were reported for the first time (to our knowledge), as well as newer data for the 15 N nuclei. 301 15 N-Labeled Et 5-oxo-2-phenyl-4-(2-phenylhydrazono)-4,5-dihydro-1 H-pyrrole-3-carboxylate is synthesised by azocoupling of diazotised aniline (using Na 15 NO 2 , 99% 15 N) with Et 4,5-dihydro-5-oxo-2-phenyl-( 1 H)-pyrrole-3-carboxylate.…”