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Updated: Dec 7, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Building C(sp3 ) Molecular Complexity on 2,2'-Bipyridine and 1,10-Phenanthroline in Rhenium Tricarbonyl Complexes
Rebeca Arevalo1,2, Ramón López3, Larry R Falvello4
1Departamento 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.
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