We have recently reported on the first cage-like in,in/out,out dibridgehead diphosphine 1  with 30-membered rings that has been obtained by a synthetic route involving olefin metathesis in the coordination sphere of a platinum complex in yields up to 91%.[1],[2],[3],[4].Thermal inversion of one bridgehead phosphorous atom leads to the in/out isomer 2  , which represents a stable isomer retaining the basic cage structure. Both 1  and 2  undergo fast conformational changes by in/out isomerization via a concerted disrotatory bridgehead motion.Herein, we describe an unusual third isomer 3  obtained from the metathesis/decomplexation sequence, consisting of two macrocyclic ring phosphines which are connected by a (CH2)14 chain linker. Moreover, the complexation behavior of the in,in/out,out cage diphosphine 1 and its ability to serve as a solvent molecule scavenger are presented.[1] Nawara, A. J.; Shima, T.; Hampel, F.; Gladysz, J. A. J. Am. Chem. Soc. 2006  , 128, 4962.[2] Stollenz, M.; Barbasiewicz, M.; Nawara-Hultzsch, A. J.; Fiedler, T.; Laddusaw, R. M.; Bhuvanesh, N.; Gladysz, J. A. Angew. Chem. 2011  , 123, 6777; Angew. Chem. Int. Ed. 2011  , 50, 6647.[3] Stollenz, M.; Bhuvanesh, N.; Reibenspies, J. H.; Gladysz, J. A. Organometallics 2011  , 30, 6510.[4] Nawara-Hultzsch, A. J.; Stollenz, M.; Barbasiewicz, M.; Szafert, S.; Lis, T.; Hampel, F.; Bhuvanesh, N.; Gladysz, J. A. Chem.�Eur. J. 2014  , DOI:  10.1002/chem.201304419.

Macrobicyclic diphosphines from olefin metathesis in platinum coordination spheres: Synthesis, structures, and reactivity of three stable isomers

248th National Meeting (2014)

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