SYNTHESIS AND STEREOCHEMICAL NONRIGIDITY OF ISOMERIC ZN(II) BIS-[N-ISOPROPYLOXY(MERCAPTO)NAPHTHALDIMINATES]

Citation
Vi. Minkin et al., SYNTHESIS AND STEREOCHEMICAL NONRIGIDITY OF ISOMERIC ZN(II) BIS-[N-ISOPROPYLOXY(MERCAPTO)NAPHTHALDIMINATES], Russian chemical bulletin, 44(11), 1995, pp. 2168-2171
Citations number
14
Categorie Soggetti
Chemistry
Journal title
ISSN journal
10665285
Volume
44
Issue
11
Year of publication
1995
Pages
2168 - 2171
Database
ISI
SICI code
1066-5285(1995)44:11<2168:SASNOI>2.0.ZU;2-O
Abstract
Kinetics and reaction mechanisms governing inversion of the tetrahedra l configuration at the metal center in the series of bis-chelate Zn(II ) complexes of 3,2-, 1,2-, and 2,1-oxy(mercapto)naphthaldimines, respe ctively 4-6, have been studied with the use of dynamic H-1 NMR spectro scopy. A polytopal rearrangement of the diagonal twist type has been f ound to be an energetically preferable pathway of the inversion reacti on for complexes 4 and 5 with a ZnN2O2 coordination site? whereas the inversion reaction for complexes with a ZnN2S2 coordination site occur s by an intramolecular dissociation-recombination pathway that involve s cleavage of a Zn-N coordination bond. In the case of complexes 6, th e inversion reaction is governed mainly by intramolecular degenerate l igand exchange reactions.