13C NMR spectral data for some N,N‐dialkylbenzylamines and their cyclopalladated complexes

Barr, Neal; Dyke, S.F.; Frost, Raymond

doi:10.1002/mrc.1270220502

Cited by 27 publications

(2 citation statements)

References 8 publications

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“…For 2-aryl-2-oxazolines (HL), the signal of the ortho H in the coordination complexes Pd(HL) 2 Cl 2 is significantly shifted downfield (Δδ = 0.85−1.08) 27,34 compared to that in the free ligands, due to the magnetic anisotropy of the Pd atom. This observation indicates that the ortho H in the coordinated oxazoline ligand in solution is in close proximity to the metal and is above the PdN 2 Cl 2 plane . The X-ray diffraction study of the coordination complex PdCl 2 (HL) 2 (HL = 2-phenyl-2-oxazoline) determined the same position of the ortho H atoms in the solid state …”

Section: Resultsmentioning

confidence: 84%

Endo-Effect-Driven Regioselectivity in the Cyclopalladation of (S)-2-tert-Butyl-4-phenyl-2-oxazoline

et al. 2007

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Direct cyclopalladation of (S)-2-tert-butyl-4-phenyl-2-oxazoline using palladium acetate in acetic acid or acetonitrile provided a mixture of two isomeric compounds, the endo μ-AcO dimeric complex with a C(sp3)−Pd bond and the corresponding exo derivative with a C(sp2)−Pd bond, with the former being the major product. The μ-AcO dimeric complexes were converted to the corresponding μ-Cl analogues 3 and 4 by treatment with LiCl in acetone; the latter compounds were transformed to the corresponding PPh3 adducts 5 and 6. The NMR data suggested the puckered structure of the endo palladacycle in complexes 3 and 5, the twisted λ(S) conformation of the oxazoline ring in 3, 4, and 6, and the δ(S) conformation of the heterocycle in complex 5. The X-ray crystal structure of 5 confirmed the δ(S) conformation of the oxazoline ring in the solid state and the twisted conformation of the palladacycle and revealed a P-propeller chiral configuration of the PPh3 ligand. A series of ab initio quantum chemical calculations were performed on two model compounds generated by replacing the PPh3 ligands with NH3 in complexes 5 and 6. The structures and energies of the two model exo and endo isomers were calculated at the RHF, BLYP, and MP2 levels of theory with a 6-31G* basis for the light atoms and LANL2DZ ECP for the palladium and were found to be comparable. Single point coupled cluster calculations, with single double excitations (CCSD), corroborated the results.

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Section: Resultsmentioning

confidence: 84%

Endo-Effect-Driven Regioselectivity in the Cyclopalladation of (S)-2-tert-Butyl-4-phenyl-2-oxazoline

et al. 2007

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“…6 Additional bands: 2b, CH3 at 2.34; 2c, CH3 at 2.29 (6), 2.03 (3); 2d, CH3 at 2.28 (6), 2. 21 (3); 3a, H3 at 8.45 (5.5), 7.5; 3b, H3 at 8. 20 (5.5), 13.0; 3c, H3 at 8.…”

Section: *2j(pp)mentioning

confidence: 99%

Synthesis and NMR spectroscopy of cyclopalladated tertiary phosphite complexes. X-ray crystal structure of Pd(.eta.5-C5H5)[P(OPh)2(OC6H4)]

Albinati¹,

Affolter²,

Pregosin³

1990

Organometallics

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Interactions and 2D NOESY. Pd(II) and Pt(II) cylometallation chemistry

Pregosin

Wombacher

1991

Magnetic Reson in Chemistry

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Phase sensitive, 1H 2D NOESY measurements have been made on a variety of N,N′‐dimethylbenzylamine cyclopalladated complexes with coordinated ligands having pendant CH moieties. For 8‐methylquinoline and benzo [h] quinoline it can be shown that the quinoline‐methyl and benzoquinoline CH‐10 moieties, respectively, reside in a pseudo fifth coordination position above the square planar complex. This information arises primarily from NOEs from one NCH3 and H3′, the proton ortho to the PdC bond. Similar NOESY studies have also been carried out for (i) a cyclopalladated aliphatic analog based on Pd(NO3(L){N(CH3)2CH2C (CH3)(OCH3)CH2} and (ii) a cyclopalladated phosphite (C∩oP), of the form Pd(NO3)(L){P(OEt)2OC6H4}. New platinum complexes of the type trans‐[PtCl2L (tertiary phosphine or tertiary arsine)] are presented, and the spin–spin coupling constants from the pendant CH of L to the 195Pt are discussed. Several of these complexes can exist in two geometric forms, i.e., for the phosphite complexes: P trans to N, C trans to O as against P trans to O, C trans to N. A distinction between these isomers is made using the same 1H NOESY spectra that provide information concerned with the pendant CH functions.

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¹³C NMR spectral data for some N,N‐dialkylbenzylamines and their cyclopalladated complexes

Abstract: 13C NMR data for some N,N‐dialkylbenzylamines and their chloro‐(N,N‐dialkylbenzylamine‐6,C,N)‐tri‐phenylphosphinepalladium(II) complexes are presented and simple shift parameters defined.

Cited by 27 publications

References 8 publications

Endo-Effect-Driven Regioselectivity in the Cyclopalladation of (S)-2-tert-Butyl-4-phenyl-2-oxazoline

Endo-Effect-Driven Regioselectivity in the Cyclopalladation of (S)-2-tert-Butyl-4-phenyl-2-oxazoline

Synthesis and NMR spectroscopy of cyclopalladated tertiary phosphite complexes. X-ray crystal structure of Pd(.eta.5-C5H5)[P(OPh)2(OC6H4)]

Interactions and 2D NOESY. Pd(II) and Pt(II) cylometallation chemistry

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