Summary
The reaction of [CrCl3(DMF)3] with C-meso-5, 12-dimethyl-1, 4, 8, 11-tetra-azacyclotetradecane(LM) in DMF gives a mixture ofcis-[CrLMCl2]Cl (ca. 90%) andtrans-[CrLMCl2]Cl (ca. 10%). These complexes are readily separated, as thecis-isomer is insoluble in warm methanol while thetrans-isomer is soluble. Using the dichlorocomplexes as precursors it has been possible to prepare a range ofcis-[CrLMX2]+ complexes (X=Br−, NO −3 , N −3 , NCS− and X2=bidentate oxalate) and alsotrans-[CrLMX2]+ complexes (X=Br−, H2O or NCS−). The spectroscopic properties and detailed stereochemistry of the complexes are discussed.
The aquation and base hydrolysis kinetics ofcis- andtrans-[CrLMCl2]+ have been studied at 25° C. Base hydrolysis of thecis-complex is extremely rapid with KOH =1.46×105 dm3 mol−1 at 25° C. This unusual reactivity appears to be associated with thetrans II stereochemistry of thesec-NH centres of the macrocycle. Base hydrolysis of thetrans complex with thetrans III chiral nitrogen stereochemistry is quite “normal” with kOH =1.1 dm3 mol−1 s−1 at 25° C.
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Hay, R.W., Pujari, M.P., Bembi, R. et al. The preparation and characterisation of chromium(III) complexes of C-meso-5, 12-dimethyl-1, 4, 8, 11-tetraazacyclotetradecane (LM). Aquation and base hydrolysis kinetics ofcis- andtrans-[CrLMCl2]+ . Transition Met Chem 14, 393–400 (1989). https://doi.org/10.1007/BF01032519
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DOI: https://doi.org/10.1007/BF01032519