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As substrates, three dirhodium(II) compounds were applied, tetraacetate, tetrakistrifluoroacetate, and a derivative of optically pure Mosher's acid. Due to conformational flexibility, free and complexed ligands can adopt potentially various conformations. The NMR titration experiments revealed the subsequent formation of 1:1 and 1:2 complexes, depending on the molar ratio of substrate to ligand. Conformations of free and complexed ligands were examined by the comparison of experimental and DFT gauge\u2010independent atomic orbital (GIAO) calculated chemical shifts and by the analysis of the internal energy of the compounds. For some ligand and substrate combinations, a mixture of complexes differing in ligand conformations was formed. Complexes of Mosher's acid derivative of rhodium(II) with racemic 1,2\u2010dimethylpyrrolidin and 1,2\u2010dimethylpiperidine exhibited NMR chiral recognition phenomenon, manifested by splitting of signals in <jats:sup>13<\/jats:sup>C NMR and <jats:sup>1<\/jats:sup>H,<jats:sup>13<\/jats:sup>C HSQC spectra.<\/jats:p>","DOI":"10.1002\/chir.23345","type":"journal-article","created":{"date-parts":[[2021,8,23]],"date-time":"2021-08-23T17:38:17Z","timestamp":1629740297000},"page":"660-674","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Complexation in situ of 1\u2010methylpiperidine, 1,2\u2010dimethylpyrrolidin, and 1,2\u2010dimethylpiperidine with rhodium(II) tetracarboxylates: Nuclear magnetic resonance spectroscopy, chiral recognition, and density functional theory studies"],"prefix":"10.1002","volume":"33","author":[{"given":"Agnieszka","family":"Sadlej","sequence":"first","affiliation":[{"name":"Institute of 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