title: Synthesis and Conformational Behavior of Rhodium(I) Metallohosts Derived from Diphenylglycoluril.
abstract: The design and synthesis of molecules containing both a substrate-binding cavity and a nearby catalytically active metal center is a useful approach to the development of synthetic systems that function according to the principles of enzymes. To this end the receptor molecule 2a, derived from diphenylglycoluril, was functionalized with triaryl phosphite ligands to give the receptor ligand 2d. Exchange reactions of 2d with (diketonate)Rh(CO)(2), (diketone = acetylacetone, dibenzoylmethane, or dipivaloylmethane) led to the formation of the metallohosts 3a-c, respectively. The properties and conformational behavior of these metal complexes were studied by NMR techniques. Reaction of compounds 3 with H(2) in the presence of a small excess of additional triphenyl phosphite yields the rhodium(I) hydride complex 5. The metallohosts are capable of binding dihydroxybenzene guests in their cavities by hydrogen bonding and pi-pi stacking interactions. On binding a substrate the conformational behavior of hosts 3a-c was affected considerably.
authors.affiliation: Department of Organic Chemistry, Nijmegen SON Research Center, Toernooiveld, 6525 ED Nijmegen, The Netherlands, and Department of Chemical Engineering, J. H. van't Hoff Instituut, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands.
authors.forename: Hein K. A. C.
authors.initials: HK
authors.lastname: Coolen
authors.forename: Piet W. N. M.
authors.initials: PW
authors.lastname: van Leeuwen
authors.forename: Roeland J. M.
authors.initials: RJ
authors.lastname: Nolte