Synthesis,Structure And Spectroscopic Properties Of Copper(I)-Phosphine-Nitrogen Heterocycle Mixed-ligand Complexes

1 Five mixed-ligand Cu(I) complexes all containing triphenylphospine and N- donor heterocycles ligands have been synthesized. These N-donor heterocycles ligands include imidazole(HIm), 1,2,3 ?benzotriazole(bta), 8-hydroxyquinoline(oxine), quinoline(Quin), 2,2?dipyridylamine(dpa). All of the complexes have been structurally characterized by X-ray crystal structural analysis. And the spectroscopic properties of the complexes were also explored. (1) Complex [Cu(HIm),(PPh3),](BF4) (1)crystallizes in the monoclinic space group P21/c, with a12.836(3)A, b15.089(3)A, c20.661(4) A, I3=l01.464(4)~, Z = 4. The crystal structure of 1 shows the copper atom is coordinated by a pair of HIm ligands and a pair of PPh3 ligands in a distorted 梩etrahedral N,P2 environment with Cu(1)-N(1) 2.075(2)A, Cu(1)-N(3) 2.095(2) A. Cu(1)-P(1), 2.2764(7)A and Cu(1)-P(2) 2.2803(8) A. These value are similar to those Cu(I) complexes in a same N,P-, environment. In complex (1), because of the crowd space of PPh3, the bond-angle of P- Cu-P is 124.02(3)0, which is larger than those in the analogous complexes, such as [Cu(py),(PPh4,]~ and [Cu(pydz),(PPh3)2]~. While the bond angle of N-Cu-N is 100.29(10)0, smaller than the analogous. It is due to the steric bulkiness from the hexatomic ring of the pyridine or pyrazine in complexes [Cu(py)-,(PPh3)2]~ and [Cu(pydz),(PPh4,]~, while the ligand imidazole is a fivemembered ring. (2) The complex [Cu4(bta)3(PPh3)4][Cu(PPh3)3](BF4)2 (2)crystallizes in the trigonal space group P3cl, with a17.430(2)A, b17.430(2) A, c26.945(5) A, a 900, 13900 y 120拁, Z=6. The crystal structure of 2 contains two complexes cations, namely a novel unit [Cu4(bta)3(PPh3)4]~ with 3-fold symmetry, and a known unit [Cu(PPh3)3] ~. In [Cu4(bta)3(PPh3)4]~, a tetrahedrally coordinated copper(I) ion is surrounded by three trigonally coordinated copper(I) ions held by bridging bta ligands, and the ligand PPh3 terminates it to a tetrahedral array, shaping a reversed umbrella structure. Each surrounding copper ion is three-coordinated by two nitrogen atoms in two different bta ligands and a phosphine atom in PPh3. (3) The complex [Cu(PPh3)7(Quin)J(BF4) (3) crystallizes in the monoclinic space ?In ? ih~)~ 2001 ~zH~{~L~ group P211c, with a~19.445(5)A, b11.878(3) A, c17.637(4) A, I3~94.009(4)O, Z= 4. Structure analysis reveals that the copper(I) atom is coordinated by two PPh3 ligands and one quinoline ligand in a three-co-ordinate way. Bond angles of N(1)-Cu(1)-P(2), N(1)-Cu(1)-P(1) and P(2)-Cu(1)-P(1) are 117.47(7)0, 110.15(7)~ and 128.50(3)0 respectively. These values are similar to each other, and the sum of them is close to 3600. So, the nuclear of CuNP-, is in a trigonal plane. (4) The complex [Cu(PPh3)2(oxine)] (BF4) (4)crystallizes in the monoclinic space group P21/n, with a~ 11 .372(3)A, b~22. 1 71(5)A, c 16.038(4)A, J3~97.942(5)~, Z 4. Structure analysis shows that the copper(I) is coordinated by two PPh3 ligands and one bidentate 8- hydroxyquinoline ligand, two phosphine atoms and a oxygen atom and a nitrogen atom from oxine ligate in a distorted tetrahedral arrangement. This is a novel complex with CuONP2 geometry. The bond length of Cu-O is 2.2727(18) A, Cu 桸 is 2.037(2) A, and Cu-P is 2.2549(7) A and 2.2675(8) A respectively. (5) The complex [Cu(dpa)(PPh3)2](BF4).CH3CN.CHCI3 (5) crystallizes in the...