2 NOVEL TYPES OF METAL-COMPLEXES DERIVED FROM TRIPOD AMINES AND ACETYLACETONE

Condensations of tris(2-aminoethyl)amine (tren) with acetylacetone (ac ac) give two different types of complexes, depending upon the coexisti ng metal ions; one contains two tridentate ligands which have beta-ket oimine moieties at all primary amino groups of tren, and the other has a pentadentate ligand having a beta-ketoimine moiety at one of the th ree amino groups of tren. The Sr2+, Ca2+, Mg2+, and Mn2+ ion give the former type complexes and Cu2+, Co3+, and Zn2+ give the latter. The cr ystal structures of all the complexes have been characterized by X-ray analyses. Crystal data for the Sr2+ complexes: SrC90H106N106B2, a = 1 2.32(1), b = 17.65(2), c = 10.98(1) Angstrom, alpha = 99.04(9), beta = 104.53(9), gamma = 104.47(9)degrees, V = 2176(4) Angstrom(3), triclin ic, P (1) over bar, Z = 1. For the Ca2+ complex: CaC50H106N8O6B2, a = 12.882(2>, b = 15.904(4), c = 11.314(4) Angstrom, alpha = 102.37(2), b eta = 94.70(2), gamma = 110.16(1)degrees, V = 2094(1) Angstrom(3), tri clinic, P (1) over bar, Z = 1. For the Mg2+ complex: MgC90H106N8O6B2, a = 12.839(4), b = 15.773(6), c = 11.199(3) Angstrom, alpha = 101.50(3 ), beta = 95.35(3), gamma = 110.24(2)degrees, V = 2052(1) Angstrom(3), triclinic, P (1) over bar, Z = 1. For the Mn2+ complex: MnC50H106N8O6 B2, a = 12.858(3), b = 15.818(6), c = 11.210(3) Angstrom, alpha = 101. 80(2), beta = 95.06(2), gamma = 110.20(2)degrees, V = 2063(1) Angstrom (3), triclinic, P (1) over bar, Z = 1. For the Cu2+ complex: CuC35H43N 4OB, a = 11.060(5), b = 15.874(4), c = 17.886(4) Angstrom, beta = 91.8 9(3)degrees, V = 3138(1) Angstrom(3), monoclinic, P2(1)/n, Z = 4. For the Zn2+ complex: ZnC35H43N4OB, a = 11.084(4), b = 15.955(3), c = 17.8 38(2) Angstrom, beta = 92.11(2)degrees, V = 3152(1) Angstrom(3), monoc linic, P21/n, Z = 4. For the Co3+ complex: CoC35H43N4OBCl, a = 17.996( 2), b = 10.150(5), c = 19.741(2) Angstrom, beta = 113.460(7)degrees, V = 3307(1) Angstrom(3), monoclinic, P2(1)/c, Z = 4. The selectivity of the products is discussed in terms of the ionic size and the affinity between the metal ion and the donor atoms. The reaction of acac with tris(3-aminopropyl)amine in the presence of the Ca2+ ion was also perf ormed, the first type of the structure was found. The structure is als o confirmed by X-ray analysis. Crystal data: CaC96H124N8O6B2, a = 12.3 64(4), b = 16.502(6), c = 12.008(5) Angstrom, alpha = 103.62(3), beta = 91.14(3), gamma = 110.09(2)degrees, V = 2222(1) Angstrom(3), triclin ic, P (1) over bar, Z = 1.