Reactions of Nitrogen Donors with Cycloheptatrienylidene Complexes: Metal Coordination versus Nucleophilic Attack on the Carbene Ligand
Cycloheptatrienylidene (CHT)–palladium complexes may react with N-donor molecules, showing two different pathways of reaction, either nucleophilic attack on the CHT ligand or coordination to the metal center. The first variant leads to a formation of water-soluble η 3 -cycloheptatrienyl complexes, a...
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Veröffentlicht in: | Organometallics 2012-12, Vol.31 (23), p.8249-8256 |
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Hauptverfasser: | , , , , , |
Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | Cycloheptatrienylidene (CHT)–palladium complexes may react with N-donor molecules, showing two different pathways of reaction, either nucleophilic attack on the CHT ligand or coordination to the metal center. The first variant leads to a formation of water-soluble η 3 -cycloheptatrienyl complexes, as in the case of 3,5-lutidine or 3-chloropyridine. Reaction with 2,6-lutidine, on the other hand, yields monomeric pyridine-substituted CHT–Pd compounds comparable to NHC–PEPPSI complexes. Reaction with 1-methylimidazole yields both a dimeric water-soluble cycloheptatrienyl palladium complex and a monomeric CHT–Pd compound, depending on the conditions of the reaction. Furthermore, a subsequent formation of a Pd3-sandwich type complex was observed, which has been determined by single-crystal X-ray diffractometry. The nucleophilic attack of morpholine on the CHT ligand reveals another possible reaction path: removal of the CHT ligand from the metal under formation of a tropylidenimmonium cation. |
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ISSN: | 0276-7333 1520-6041 |
DOI: | 10.1021/om300867g |