Macrocycles with a single pendant arm: synthesis of N-R-(1,4,7-triazacyclononane) [L, R = 4-but-1-ene; L′, R = 3-prop-1-ene]: Synthesis of the CuI complex [CuL]I and synthesis and crystal structure of the CII complex [CuL2][BPh4]2 and the μ-hydroxy bridged CII dimer [LCu(μ-OH)2CuL] [BPh4]2

We report a general method for the preparation of mono-N-substituted derivatives of [9]aneN3. The method is exemplified by the synthesis of the macrocyclic ligand N-4-but-l-ene-1,4,7-triazacyclononane, L, which has a single pendant alkene arm. We report the synthesis of three copper complexes of L: [CuIL]I, [CuIIL2][BPh4]2 (1) and [LCuII(OH)2CuIIL][BPh4]2·2(MeCN) (2). The structures of 1 and 2 have been determined; 1 C68H82BCuN3 monoclinic, P21n, a= 13.0529(8) A, b= 18.008(1) A, c= 13.423(1) A, β = 111.720(6)°, Z=2; 2 C72H90B2CU2N8O2, triclinic, Pi, a = 11.487(i)A, b= 12.870(1) A, c = 12.867(1)A, α = 106.807(6)°β = 101.833(6)°, γ = 105.859(6)°, Z= 1.