¹H, ¹³C, ¹⁵N and ¹⁹⁵Pt NMR studies of Au(III) and Pt(II) chloride organometallics with 2‐phenylpyridine

Abstract

(1)H, (13)C, (15)N and (195)Pt NMR studies of gold(III) and platinum(II) chloride organometallics with N(1),C(2')-chelated, deprotonated 2-phenylpyridine (2ppy*) of the formulae [Au(2ppy*)Cl(2)], trans(N,N)-[Pt(2ppy*)(2ppy)Cl] and trans(S,N)-[Pt(2ppy*)(DMSO-d(6))Cl] (formed in situ upon dissolving [Pt(2ppy*)(micro-Cl)](2) in DMSO-d(6)) were performed. All signals were unambiguously assigned by HMBC/HSQC methods and the respective (1)H, (13)C and (15)N coordination shifts (i.e. differences between chemical shifts of the same atom in the complex and ligand molecules: Delta(1H)(coord) = delta(1H)(complex) - delta(1H)(ligand), Delta(13C)(coord) = delta(13C)(complex) - delta(13C)(ligand), Delta(15N)(coord) = delta(15N)(complex) - delta(15N)(ligand)), as well as (195)Pt chemical shifts and (1)H-(195)Pt coupling constants discussed in relation to the known molecular structures. Characteristic deshielding of nitrogen-adjacent H(6) protons and metallated C(2') atoms as well as significant shielding of coordinated N(1) nitrogens is discussed in respect to a large set of literature NMR data available for related cyclometallated compounds.

1H, 13C and 15N nuclear magnetic resonance coordination shifts in Au(III), Pd(II) and Pt(II) chloride complexes with phenylpyridines

“…Particularly, it can be concluded from the published 1 [16,24,26,39,40] complexes (L = py, 4-methyl-py, 4-tert-butyl-py, 4-chloro-py, 4-bromo-py, 4-methoxy-py, 4-aminopy, 4-(dimethylamino)-py, 4-cyano-py, 4-acetyl-py, py-4-carboxylic acid, methyl py-4-carboxylate, 3-methyl-py, 3-fluoro-py, 3-chloropy, 3-bromo-py, 3-iodo-py, 3-methoxy-py, 3-hydroxymethyl-py, py-3-carboxylic acid, 2-methyl-py, 2-hydroxy-py, 3,5-dimethylpy, 2,4-dimethyl-py, 2,5-dimethyl-py and py-3,5-dicarboxylic acid).…”

“…[23] 13 C NMR spectra were reported for an unknown isomer of [Pt(4ppy) 2 Cl 2 ] (only CH carbons, unassigned), [16] [Pd(4ppy) 2 (bpy)](NO 3 ) 2 , [18] [Pt(3ppy) 2 (bpy)](PF 6 ) 2 and [Pt(4ppy) 2 (bpy)](PF 6 ) 2 , [23] while those of 15 N for [Pd(2ppy)(phen)(CH 3 )]CF 3 SO 3 [12] and [Pd(2ppy)(phen)(CH 2 CH 3 )]CF 3 SO 3 . [17] In this work, we report the 1 H, 13 [24 -25] picolines, [26] 2,2 -bipyridine, 1,10-phenanthroline and their methyl or phenyl derivatives [24,25,27] as well as quinolines. [28] Particularly, to the best of our knowledge, this is the first study, where the full sets of 1 H, 13 C and 15 N NMR spectral parameters are compared for the respective trans-and cis-isomers of a Pd(II)-azine complex (in contrast to Pt(II), being more common case).…”

“…The pulse sequences were the same as on our previous NMR studies on Au(III), Pd(II) and Pt(II) chloride complexes with pyridine [24,25] and picolines. [26] As references were used tetramethylsilane (TMS: 1 H, 13 C) and external CH 3 NO 2 ( 15 N). The accuracy and reproducibility of the obtained δ 15N chemical shifts were ca.…”

“…The methodology of 15 N, 1 H and 13 C shielding constants calculations, performed with the Gaussian 03 software, [31] was generally the same as described in our recent report on the Pd(II) and Pt(II) complexes with picolines. [26] The respective chemical shifts were then obtained by their substracting from the shielding constants of reference compounds (CH 3 NO 2 for 15 N, TMS for 1 H and 13 C), evaluated with an identical method. On each computational procedure (i.e.…”

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

“…This study follows our recent researches on analogous coordination and organometallic compounds with pyridine, [10 -12] picolines, [13] phenylpyridines, [14,15] 2,2 -bipyridine, 1,10-phenanthroline and their methyl or phenyl derivatives, [10,11,16] as well as quinolines. [17] …”