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The amido rhenium trioxides of composition (iPr2N)ReO3, (iPrCyN)ReO3 and(Cy2N)ReO3 (Cy = cyclohexyl) were synthesized in a one pot reaction startingfrom Re2O7, Me3SiCl and the corresponding amines (iPr)2NH, (iPr)(Cy)NH, and(Cy)2NH, respectively. In the solid state the amido ligands of all threecomplexes are asymmetrically coordinated to the ReO3 core allowing for oneshort Re-H-C contact in each case which might indicate the presence ofbeta-agostic interaction. However, analysis of the charge density distributionprovided us clear-cut criteria that beta-agostic interactions are suppressed bythe trans-influence of the oxo-groups. Comparison with structurally relatedtetra-coordinated d0 titanium amido complexes highlighted a systematic concepthow the extent of beta-agostic interactions in these complexes can becontrolled by reducing the trans-influence of the co-ligands. We thereforesuggest to employ the expression "hindered agostic interactions" in cases wherecovalent M-H-C are in principle supported by vacant coordination sites atLewis-acidic metal centers but are actually hindered for electronic reasons. Wefurther point out that electronic hindrance originating from the transinfluencemight be overruled by changing the s/p-donor characteristics of ligands.

Amido Rhenium Trioxides: Cases of Hindered Agostic C-H-M Interactions?