Ruthenium(II) pentamethylcyclopentadienyl half-sandwich carbene complexes with polypyridyl ligands
| Autor: | Gabriele Albertin, Mauro Trevisan, Jesús Castro, Marco Bortoluzzi, Stefano Antoniutti |
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| Rok vydání: | 2017 |
| Předmět: |
Materials Chemistry2506 Metals and Alloys
chemistry.chemical_element Acetylide Carbene Diazoalkane Half-sandwich Polypyridyl Ruthenium Biochemistry Physical and Theoretical Chemistry Organic Chemistry Inorganic Chemistry Protonation Crystal structure 010402 general chemistry Photochemistry 01 natural sciences Medicinal chemistry chemistry.chemical_compound Materials Chemistry Settore CHIM/03 - Chimica Generale e Inorganica 010405 organic chemistry 0104 chemical sciences chemistry |
| Zdroj: | Journal of Organometallic Chemistry. 848:1-9 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/j.jorganchem.2017.07.022 |
| Popis: | Polypyridyl complexes [RuCl(η5-C5Me5)(N–N)] (1–4) [N–N 2,2′-bipyridine (bpy) (1), 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me2bpy) (2), 1,10-phenanthroline (phen) (3) and 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen) (4)] were prepared by reacting [RuCl2(η5-C5Me5)]2 with Zn dust in the presence of polypyridyl ligands. Unlike the related [RuCl(η5-C5Me5)(L1)(L2)]+ [L1, L2 = P(OR)3, PPh3] derivatives with P-donor ligands, treatment of chloro compounds 1–4 with diazoalkanes Ar1Ar2CN2 afforded polypyridyl carbene complexes [Ru(η5-C5Me5)( CAr1Ar2)(N–N)]BPh4 (5–8) [Ar1 = Ar2 = Ph (a), Ar1 = Ph, Ar2 = p-tolyl (b)]. Comparative DFT studies of the formation of metallacarbenes from aromatic diazoalkanes are reported. Phosphite complex [Ru(η5-C5Me5)(bpy){P(OEt)3}]BPh4 (9) and acetylide derivatives [Ru(η5-C5Me5)(C CAr)(bpy)] (10, 11) [Ar = Ph (10), p-tolyl (11)] were also obtained by substitution of the carbene in 5–8. Unstable vinylidene cations [Ru(η5-C5Me5){ C C(H)Ar](bpy)]+ (12, 13) were formed by protonation with HBF4•Et2O of acetylide species 10, 11. The complexes were characterized spectroscopically (IR and 1H, 13C, 31P NMR) and by X-ray crystal structure determination of [Ru(η5-C5Me5){ C(Ph)(p-tolyl)}(bpy)]BPh4 (5b). |
| Databáze: | OpenAIRE |
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