¹H, ¹³C, ¹⁹⁵Pt and ¹⁵N NMR structural correlations in Pd(II) and Pt(II) chloride complexes with various alkyl and aryl derivatives of 2,2′‐bipyridine and 1,10‐phenanthroline

Abstract

(1)H, (13)C, (195)Pt and (15)N NMR studies of platinide(II) (M = Pd, Pt) chloride complexes with such alkyl and aryl derivatives of 2,2'-bipyridine and 1,10-phenanthroline as LL = 6,6'-dimethyl-bpy, 5,5'-dimethyl-bpy, 4,4'-di-tert-butyl-bpy, 2,9-dimethyl-phen, 2,9-dimethyl-4,7-diphenyl-phen, 3,4,7,8-tetramethyl-phen, having the general [M(LL)Cl(2)] formula were performed and the respective chemical shifts (δ(1H), δ(13C), δ(195Pt), δ(15N)) reported. (1)H high-frequency coordination shifts (Δ(coord)(1H) = δ(complex)(1H)-δ(ligand)(1H)) mostly pronounced for nitrogen-adjacent protons and methyl groups in the nearest adjacency of nitrogen, as well as (15)N low-frequency coordination shifts (Δ(coord)(15H) = δ(complex)(15H)-δ(ligand)(15H)) were discussed in relation to the molecular structures.

Heteropolymetallic Complexes Linked to a 9,10-Dihydroanthracenyl Frame. Ruthenium as Active Spectator for Palladium Reactivity

“…The coordination of the diamine fragment to the metal was proven by { 1 H, 15 N}-HMBC NMR experiments at natural abundance of the 15 N isotope for the ligand 2 and complexes 4 and 5 (unfortunately, complex 6 was not soluble enough for this kind of experiment). As reported for Pd(II) complexes containing N-donor ligands, the nitrogen chemical shifts for complexes are shielded (by ca. 5–7 ppm) in relation to the free ligand (Figure S5 in the Supporting Information).…”

Predesigned Metal-Anchored Building Block for In Situ Generation of Pd Nanoparticles in Porous Covalent Organic Framework: Application in Heterogeneous Tandem Catalysis

“…In the case of Bpy-PdCl 2 , the signal at 67.6 ppm corresponds to the Pd-metal-coordinated pyridinic nitrogen. In contrast, the signal corresponding to the pyridinic nitrogen of Pd@TpBpy appears at 127.1 ppm, which is very comparable to the signals of the pyridinic nitrogens of TpBpy (128.5 ppm), suggesting the pyridinic nitrogens of Pd@TpBpy are not strongly coordinated to the Pd-metal centers as in the Bpy-PdCl 2 complex. , However, the significant upfield shift (1.4 ppm) of the pyridinic nitrogens in the case of Pd@TpBpy compared to that of TpBpy suggests that the Pd nanoparticles in Pd@TpBpy are stabilized by the weak nonbonding interactions with the pyridinic nitrogens of the bipyridinic unit. This result also confirms our initial speculation that during the course of Pd@TpBpy formation, the breakage of the PdN bond of the Bpy-PdCl 2 complex takes place, which leads to the in situ synthesis of Pd nanoparticles in the Pd@TpBpy hybrid.…”

High-Frequency 13C and 29Si NMR Chemical Shifts in Diamagnetic Low-Valence Compounds of TlI and PbII: Decisive Role of Relativistic Effects

“…The D3 dispersion correction by Grimme was employed during the optimizations. This level of theory has been justified by the previous studies of metal complexes. − The implicit conductor-like screening model solvent model was adopted throughout the geometry optimizations of the experimentally prepared compounds, with solvent parameters selected according to the experimental setup. The structures of theoretically predicted model compounds were optimized in vacuo, that is, without implicit solvent treatment.…”