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While their buried volume (%<jats:italic>V<\/jats:italic><jats:sub>bur<\/jats:sub>) was calculated to get insight into the steric properties, [LNi(CO)<jats:sub>3<\/jats:sub>] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS\u2010NOCV (extended\u2010transition\u2010state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the \u03c3\u2010 and \u03c0\u2010contributions to the <jats:sc>L\u2212<\/jats:sc>M interaction. Au<jats:sup>I<\/jats:sup> coordination compounds of selected examples were prepared and characterized by single crystal X\u2010ray diffraction. 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