|
|||||
|
|
Building C(sp3) Molecular Complexity on 2,2′-Bipyridine and 1,10-Phenanthroline in Rhenium Tricarbonyl Complexes |
|
| Authors: | Dr Rebeca Arevalo Dr Ramón López Prof Larry R Falvello Dr Lucía Riera Dr Julio Perez |
| Institution: | 1. Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, Julián Clavería, 8, 33006 Oviedo, Spain
Current address: Department of Chemistry and Chemical Biology, University of California, Merced, 5200 N. Lake Road, 95343 Merced, CA, USA;2. Departamento de Química Física y Analítica, Universidad de Oviedo, Julián Clavería, 8, 33006 Oviedo, Spain;3. Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón (ICMA), Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain;4. Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, Julián Clavería, 8, 33006 Oviedo, Spain Centro de Investigación en Nanomateriales y Nanotecnología-CINN, CSIC- Universidad de Oviedo-Principado de Asturias, Avda. de la Vega 4–6, 33940 El Entrego, Spain;5. Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, Julián Clavería, 8, 33006 Oviedo, Spain |
| Abstract: | The reactions of Re(N-N)(CO)3(PMe3)]OTf (N-N=2,2′-bipyridine, bipy; 1,10-phenanthroline, phen) compounds with tBuLi and with LiHBEt3 have been explored. Addition to the N-N chelate took place with different site-selectivity depending on both chelate and nucleophile. Thus, with tBuLi, an unprecedented addition to C5 of bipy, a regiochemistry not accessible for free bipy, was obtained, whereas coordinated phen underwent tBuLi addition to C2 and C4. Remarkably, when LiHBEt3 reacted with Re(bipy)(CO)3(PMe3)]OTf, hydride addition to the 4 and 6 positions of bipy triggered an intermolecular cyclodimerization of two dearomatized pyridyl rings. In contrast, hydride addition to the phen analog resulted in partial reduction of one pyridine ring. The resulting neutral ReI products showed a varied reactivity with HOTf and with MeOTf to yield cationic complexes. These strategies rendered access to ReI complexes containing bipy- and phen-derived chelates with several C(sp3) centers. |
| Keywords: | 1 10-phenanthroline 2 2′-bipyridine carbonyl ligands reactivity of coordinated ligands rhenium |