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The term "atropisomerism" technically refers to conformers which can be isolated as separate chemical species as a result of restricted rotation about a single bond [IUPAC Compendium of Chemical Terminology 2nd ed.; 1997]. We stretch this definition slightly in applying it to L4Pd(endo-L2) and L4Pd(exo-L2), which are isolable as a result of restricted rotation about various single bonds in particular ligand orientations.
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The term "co-conformation" is generally used to refer to the relative positions of mechanically interlocked components with respect to each other [Fyfe, M. C. T.; Glink, P. T.; Menzer, S.; Stoddart, J. F.; White, A. J. P.; Williams, D. J. Angew. Chem., Int. Ed. Engl. 1997, 36, 2068-2070]. However, since the two components in LAPd(endo-L2) and L4Pd(exo-L2) are connected by a continuous sequence of covalent and coordination bonds, in this case "conformation" is a sufficient descriptor.
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The hydrogenation conditions employed in Routes I and III led to a complex mixture when applied to the products of metathesis in Route II. Not only was significant decomplexation of the somewhat strained noninterlocked double macrocycle complex observed but also the resulting free monodentate ligand, L5, was degraded, presumably by hydrogenolysis of the benzyl ether moieties. Although the use of Pd EnCat did not prevent the ligand decomplexation during the hydrogenation step, it significantly reduced the degradation of the free monodentate macrocycle [Bremeyer, N.; Ley, S. V.; Ramarao, C.; Shirley, I. M.; Smith, S. C. Synlett 2002, 1843-18441.
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