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The synthesis of small azamacrocycles bearing pendant aromatic functionalities. The crystal structures of [Cu(L-1)(2)](PF6)(2), [(L-1)CuCl2], [Cu(L-6)(NO3)(2)] and [Cu-2(L-7-H)(2)(OH2)(2)](PF6)(2)center dot 3H(2)O (L-1 = N-(mesitylethyl)-1,4,7-triazacyclononane, L-6 = N-(4-hydroxymethylbenzyl)-1,4,7-triazacylcononane, L-7 = N-(4-benzylcarboxylic acid)-1,4,7-triazacylcononane)

Lookup NU author(s): Professor Andrew Benniston


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A simple synthetic procedure for the mono- or di-functionalization of tri- and tetra-azamacrocycles with electron rich arenes has been developed. Specifically, 1,4,7-triazacyclononane (tacn), 1,4,7, 10-tetraazacyclododecane (cyclen) and 1 4,8,11-tetraazacyclotetradecane (cyclam) react with 2,4,6-trimethylstyrene in the presence of n-butyllithium to give, respectively N-(mesitylethyl)-1,4,7-triazacyclononane (L-1), N-(mesitylethyl)-1,4,7,10-tetraazacyclododecane (L-4), and N-(mesitylethyl)-1,4,8,11-tetraazacyclotetradecane (L-5). In contrast, when styrene itself or p-vinylanisole are used as the Michael acceptor with 1,4,7-triazacyclononane. the N',N" product is formed, respectively N',N"-bis(phenylethyl)-1,4,7-triazacyclononane (L-2) and N',N"-bis(p-methoxyphenylethyl)-1,4,7-triazacyclononane (L-3). Using conventional mono-functionalization techniques, the phenyl derivatives N-(4-hydroxymethylbenzyl)-1,4,7-triazacyclononane (L-6) and N-(4-benzylcarboxylic acid)-1, 4,7-triazacyclononane (L,) have also been synthesised. A series of transition metal complexes of L-1 to L-7 with Ni(II), Cu(II), Zn(II) and Co(II) have been prepared. The X-ray crystal structures of [Cu(L-1)(2)](PF6)(2), [(L-1)CuCl2], [Cu(L-6)(NO3)(2)] and [Cu-2(L-7-H)(2)(OH2)(2)](PF6)(2).3H(2)O are described. In all of these complexes, coordination to the metal takes place through the macrocycle nitrogens. The crystal structure of [Cu-2(L-7-H)(2)(OH2)(2)](PF6)(2).3H(2)O reveals that it is a coordinate-polymeric material. Attempts to coordinate the pendent arenes to Rh(I) are discussed. (C) 2002 Elsevier Science Ltd. All rights reserved.

Publication metadata

Author(s): Benniston AC; Ellis D; Farrugia LJ; Kennedy R; Peacock RD; Walker S

Publication type: Article

Publication status: Published

Journal: Polyhedron

Year: 2002

Volume: 21

Issue: 3

Pages: 333-342

ISSN (print): 0277-5387

ISSN (electronic): 1873-3719

Publisher: Pergamon


DOI: 10.1016/S0277-5387(01)00994-9


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