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Details van artikel 24 van 73 gevonden artikelen
| Titel: |
HYDROGENATION OF A DELOCALIZED DIIMINATE SIX-MEMBERED CHELATE RING IN TETRAAZAMACROCYCLIC NICKEL(II) COMPLEXES BY SODIUM BOROHYDRIDE IN WATER—EFFECT OF PROTONATION-DEPROTONATION EQUILIBRIA AND STEREOSELECIVE REDUCTION |
| Auteur: |
Mochizuki, Katsura Kondo, Takesi Manaka, Shinobu Kajiwara, Takashi Ito, Tasuku |
| Verschenen in: |
Journal of coordination chemistry |
| Paginering: | Jaargang 37 (1996) nr. 1-4 pagina's 205-216 |
| Jaar: |
1996-02-01 |
| Inhoud: |
Charge delocalized diiminate six-membered chelate rings in the 5,7-dimethyl-1,4,8,11-tetraazacyclotetradecane-4,6-dienatonickel(II) ion(1) and the α,α'-bis(5,7-dimethyl-1,4,8, 11-tetraazacyclotetradeca-4,6-dienato-6-yl)-xylenedinicke(II) ion(2) were hydrogenated in aqueous media by sodium borohydride. In the reduction reactions, control of the pH of the reaction mixture was essential, and the pH of the solution was kept during the reaction at 3 and at 5-6 for hydrogenations of 1 and 2, respectively. The delocalized diiminate chelate ring is in protonation-deprotonation equilibrium with the β diimine form and the pKa of the equilibrium for 2 was determined to be 9.0 for 2a (o-xylylene bridged complex), 9.3 for 2b (m-xylylene bridged complex), and 10.0 for 2c (p-xylylene bridged complex). The appropriate pH values in the hydrogenation reactions were based on the pKa's. X-ray structure analyses on two reduction products of 1 show that the chirality of the two asymmetric carbons in the cyclam ring is of the meso-form in the major reduction product whereas that in the minor product is of the racemic form. In the major reduction product of 2, two chiral carbons in each cyclam ring take the meso-form. |
| Uitgever: |
Taylor & Francis |
| Bronbestand: |
Elektronische Wetenschappelijke Tijdschriften |
Details van artikel 24 van 73 gevonden artikelen
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