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Polymeric adducts of rhodium(II) tetraacetate with aliphatic diamines: natural abundance 13 C and 15 N CPMAS NMR investigations
Author(s) -
Jaźwiński Jarosław,
Kamieński Bohdan,
Sadlej Agnieszka
Publication year - 2013
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.4017
Subject(s) - chemistry , diamine , rhodium , adduct , nmr spectra database , chemical shift , nuclear magnetic resonance spectroscopy , covalent bond , proton nmr , density functional theory , carbon 13 nmr , stereochemistry , polymer chemistry , organic chemistry , computational chemistry , spectral line , catalysis , astronomy , physics
Complexation properties of dimeric rhodium(II) tetracarboxylates have been utilised in chemistry, spectroscopy and organic synthesis. Particularly, the combination of these rhodium salts with multifunctional ligands results in the formation of coordination polymers, and these are of interest because of their gas‐occlusion properties. In the present work, the polymeric adducts of rhodium(II) tetraacetate with flexible ligands exhibiting conformational variety, ethane‐1,2‐diamine, propane‐1,3‐diamine and their N , N ′‐dimethyl‐ and N , N , N ′, N ′‐tetramethyl derivatives, have been investigated by means of elemental analysis, 13 C CPMAS NMR, 15 N CPMAS NMR and density functional theory modelling. Elemental analysis and NMR spectra indicated the axial coordination mode and regular structures of (1 : 1) n oligomeric chains in the case of adducts of ethane‐1,2‐diamine, N , N ′‐dimethylethane‐1,2‐diamine N , N , N ′, N ′‐tetramethylethane‐1,2‐diamine and N , N , N ′, N ′‐tetramethylpropane‐1,3‐diamine. Propane‐1,3‐diamine and N , N ′‐dimethylpropane‐1,3‐diamine tended to form heterogeneous materials, composed of oligomeric (1 : 1) n chains and the additive of dirhodium units containing equatorially bonded ligands. Experimental findings have been supported by density functional theory modelling of some hypothetical structures and gauge‐invariant atomic orbital calculations of NMR chemical shifts. Copyright © 2013 John Wiley & Sons, Ltd.