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Building C(sp 3 ) Molecular Complexity on 2,2′‐Bipyridine and 1,10‐Phenanthroline in Rhenium Tricarbonyl Complexes
Author(s) -
Arevalo Rebeca,
López Ramón,
Falvello Larry R.,
Riera Lucía,
Perez Julio
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003814
Subject(s) - chemistry , hydride , medicinal chemistry , reactivity (psychology) , rhenium , pyridine , nucleophile , chelation , phenanthroline , cationic polymerization , bipyridine , regioselectivity , selectivity , ring (chemistry) , stereochemistry , polymer chemistry , catalysis , organic chemistry , crystal structure , metal , medicine , alternative medicine , pathology
The reactions of [Re(N‐N)(CO) 3 (PMe 3 )]OTf (N‐N=2,2′‐bipyridine, bipy; 1,10‐phenanthroline, phen) compounds with t BuLi and with LiHBEt 3 have been explored. Addition to the N‐N chelate took place with different site‐selectivity depending on both chelate and nucleophile. Thus, with t BuLi, an unprecedented addition to C5 of bipy, a regiochemistry not accessible for free bipy, was obtained, whereas coordinated phen underwent t BuLi addition to C2 and C4. Remarkably, when LiHBEt 3 reacted with [Re(bipy)(CO) 3 (PMe 3 )]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 Re I products showed a varied reactivity with HOTf and with MeOTf to yield cationic complexes. These strategies rendered access to Re I complexes containing bipy‐ and phen‐derived chelates with several C(sp 3 ) centers.