Macrocycles with a single pendant arm: Synthesis of N-R-(1,4,7-triazacyclononane) [L,R=4-but-1-ene; L'=3-prop-1-ene]: Synthesis of the Cu-I complex [CuL]I and synthesis and crystals structure of the Cu-II complex [CuL(2)][BPh(4)]2 and the mu-hydroxy bridged Cu-II dimer [LCu(mu-OH)(2)CuL][BPh(4)](2)

We report a general method for the preparation of mono-N-substituted derivatives of [9]aneN(3). The method is exemplified by the synthesis of the macrocyclic ligand N-4-but-1-ene-1,4,7-triazacyclononane, L, which has a single pendant alkene arm We report the synthesis of three copper complexes of L: [Cu(I)L]I, [Cu(II)L(2)][BPh(4)](2) (1) and [LCu(II)(OH)(2)Cu(II)L][BPh(4)](2) . 2(MeCN) (2). The structures of 1 and 2 have been determined; 1 C68H82BCuN3 monoclinic, P2(1)/n, a=13.0529(8)Angstrom, b=18.008(1)Angstrom, c=13.423(1)Angstrom, beta=111.720(6)degrees, Z=2; 2 C72H90B2Cu2N8O2 triclinic, P (1) over bar, a=11.487(1)Angstrom, b=12.870(1), c=12.867(1)Angstrom, a=106.807(6)degrees, beta=101.833(6)degrees, gamma=105.859(6)degrees, Z=1.