Reference

Selective derivatization of aza macrocycles

Selective derivatization of aza macrocycles. Blake, Alexander J.; Fallis, Ian A.; Gould, Robert O.; Parsons, Simon; Ross, Steven A.; Schroder, Martin (Department Chemistry, University Nottingham, Nottingham NG7 2RD, UK). Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry, (23), 4379-4387 (English) 1996 Royal Society of Chemistry. CODEN: JCDTBI. ISSN: 0300-9246. DOCUMENT TYPE: Journal CA Section: 28 (Heterocyclic Compounds (More Than One Hetero Atom)) Section cross-reference(s): 29 Functionalized compds. derived from 1,4,7-triazacyclononane, including 4,7-bis(2-hydroxy-2-methylpropyl)-1,4,7-triazacyclononane-1-carboxald ehyde (H2L1), 1-benzyl-4,7-bis(2-hydroxy-2-methylpropyl)-1,4,7-triazacyclononane (H2L2) and 1,4-bis(2-hydroxy-2-methylpropyl)-1,4,7-triazacyclononane (H2L3), were prepd. The structure of H2L3×CHCl3 (I).CHCl3 showed a disordered macrocyclic ring with the major conformer refining to a site occupancy of 0.663(8), and both disordered rings adopting a [333] conformation. The pendant alc. arms were not disordered and were found to be hydrogen bonded to a CHCl3 solvate mol. with H×××O(1) and H×××O(4) distances of 1.73 and 1.81 ? resp. The structure of Na[Cu(H2L1)(NCMe)][BF4]2[NO3] showed the copper(II) center in the [Cu(H2L1)(NCMe)]2+ cation bound to two amine donors and two alc. donors of H2L1 and to a MeCN mol. The Cu-N bond lengths lie in the range 1.984(3)-2.015(3) ?. Both alc. donors were protonated, with one short Cu-O(16) bond of 1.963(3) ? and one long Cu-O(21) bond of 2.252(3) ?. There was also a sixth longer-range interaction of the copper(II) center with the amide N [N(1)] of H2L1 at a distance of 2.611(5) ?, confirmed by the loss of planarity of the C(2)-C(9)-N(1)-C(10)-O(11)-H(10) amide fragment to give a dihedral angle between the planes defined by C(2)-C(9)-N(1) and N(1)-C(10)-O(11)-H(10) of 27.1(4)°. The structure was completed by interaction of O(11) with a Na+ ion which itself bridges to BF4- counter anions leading to a central infinite core of [Na(BF4)2]- aggregates onto which were attached the [Cu(H2L1)(NCMe)]2+ cations. The complex [Cu(H2L2)(OH2)][NO3]2 showed the six-coordinate copper(II) center bound to the three amine and two alc.There are some commonly used reagents with their cas registry numbers 1462-37-9 and 186499-21-8 in this article. donors of H2L2 and to one water mol. There were four short bonds [to N(7), N(4), O(40) and O(1)] in the range 1.961(5)-2.073(6) ? and two longer bonds to N(1) and O(70) at 2.308(5) and 2.313(5) ? resp. The H atoms of the water mol. [O(1)] and one of the pendant arms [O(40)] also made hydrogen-bonding contacts with the nitrate counter ions. .