The copper(II) complex (N-(3-methoxysalicylidene)-N’-(imidazol-4-ylmethylene)-1,3-propandiamino)copper(II) perchlorate, [Cu(HL)]ClO4 (1), reacts with sodium tetraphenylborate (NaPh(4)) in N,N-dimethylformamide to give an electrically neutral complex exhibiting a B-N bond, [Cu(LBPh(3))]. DMF(2). The syntheses and the crystal structures of 1, 2, and the N-methylimidazole adduct of 2, [Cu(LBPh(3))(N-MeIm)] (3), are reported. Crystal data : 1, triclinic, P (1) over bar, a = 11.842(5) Angstrom, b = 12.074(7) Angstrom, c = 7.000(2) Angstrom, alpha = 92.35(4)degrees, beta = 96.63(3)degrees, gamma = 115.16(3)degrees, Z = 2; 2, triclinic, P (1) over bar, a = 16.716(6) Angstrom, b = 18.148(4) Angstrom, c = 12.717(2) Angstrom, alpha = 106.31(2)degrees, beta = 104.67(3)degrees, gamma = 65.20(3)degrees, Z = 4; 3, monoclinic, P2(1)/n, a = 11.945(8) Angstrom, b = 12.025(9) Angstrom, c = 23.638(4) Angstrom, beta = 99.14(3)degrees, Z = 4. The most striking feature of 2 and 3 is the formation of a B-N bond, in which the boron atom bonds to the nitrogen atom of the imidazolate moiety of the copper(II) complex and to three carbon atoms of the phenyl groups.