A set of compartmental pyrazole-based ligands with appended NHC donors has been synthesized and isolated as [H4L]Cl-3 and [H3L](PF6)(2) salts. Dinuclear (allyl)palladium complexes of these ligands are conveniently accessible via the in situ prepared silver species. Three complexes [(allyl)(2)Pd2L]PF6 and one derivative [(methallyl)(2)Pd2L]PF6 have been characterized crystallographically, which revealed that the metal ions are positioned in close proximity [d(Pd center dot center dot center dot Pd) = 3.97-4.05 angstrom], with two possible mutual orientations of the (meth)allyl ligands within the dimetallic pocket. NMR spectroscopy shows slow interconversion of these isomers (k = 0.05-0.4 s(-1)), where the (meth)allyl ligands are detached trans to the carbene during this eta(3)-eta(1)-eta(3) dynamic process. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).
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Univ Jaume 1, Inst Adv Mat INAM, Av Vicente Sos Baynat S-N, Castellon de La Plana 12071, SpainBarcelona Inst Sci & Technol, Inst Chem Res Catalonia ICIQ, Avinguda Paisos Catalans 16, Tarragona 43007, Spain
Peris, Eduardo
Poyatos, Macarena
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Univ Jaume 1, Inst Adv Mat INAM, Av Vicente Sos Baynat S-N, Castellon de La Plana 12071, SpainBarcelona Inst Sci & Technol, Inst Chem Res Catalonia ICIQ, Avinguda Paisos Catalans 16, Tarragona 43007, Spain
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Univ Ca Foscari, Dipartimento Sci Mol & Nanosistemi, Calle Larga S Marta, I-30129 Venice, ItalyUniv Ca Foscari, Dipartimento Sci Mol & Nanosistemi, Calle Larga S Marta, I-30129 Venice, Italy
Canovese, Luciano
Visentin, Fabiano
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Univ Ca Foscari, Dipartimento Sci Mol & Nanosistemi, Calle Larga S Marta, I-30129 Venice, ItalyUniv Ca Foscari, Dipartimento Sci Mol & Nanosistemi, Calle Larga S Marta, I-30129 Venice, Italy
Visentin, Fabiano
Levi, Carlo
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Univ Ca Foscari, Dipartimento Sci Mol & Nanosistemi, Calle Larga S Marta, I-30129 Venice, ItalyUniv Ca Foscari, Dipartimento Sci Mol & Nanosistemi, Calle Larga S Marta, I-30129 Venice, Italy
Levi, Carlo
Santo, Claudio
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Univ Ca Foscari, Dipartimento Sci Mol & Nanosistemi, Calle Larga S Marta, I-30129 Venice, ItalyUniv Ca Foscari, Dipartimento Sci Mol & Nanosistemi, Calle Larga S Marta, I-30129 Venice, Italy