Chemistry of Transition Metal Complexes Containing Polydentate Nitrogen Ligands

• Main Authors: Yung-Sheng Yen, 嚴詠聖
• Other Authors: Jhy-Der Chen
• Format: Others
• Language: zh-TW
• Published: 2001
• Online Access: http://ndltd.ncl.edu.tw/handle/19726124986479543651

碩士 === 中原大學 === 化學研究所 === 89 === The complex cis-[Mo2(HDpyF)2(CH3CN)4][BF4]4, 1, was prepared by reaction of Mo2(DpyF)4 with excess HBF4 in THF. The reactions of 1 with pyridine afforded the complex trans-[Mo2(DpyF)2(py)4][BF4]2, 2. Their UV-vis and 1H-NMR spectra have been recorded and their structures have been determined. Crystal data for 1: space group Cmca, a = 38.003(3) Å, b = 12.847(2) Å, c = 22.023(2) Å, V = 10752(2) Å3, Z = 8, with final residuals R1 = 0.0504 and wR2 = 0.1454. The two Mo atoms are bridged by two HDpyF neutral ligands. The amine groups of the two HDpyF ligands lie close to and interact with the Mo atoms, giving rise to two N-H---Mo(II) agostic interactions. Crystal data for 2: space group P21/n, a = 10.920(1) Å, b = 14.162(1) Å, c = 17.012(1) Å, β = 99.378(1) □, V = 2595.8(2) Å3, Z = 2, with final residuals R1 = 0.0443, wR2 = 0.1029. Reaction of MnCl2 with HDMpyF afforded the complex MnCl2(HDMpyF)2, 3. Crystal data for 3: space group C2/c, a = 23.719(2) Å, b = 11.548(1) Å, c = 14.342(1) Å, β = 124.07(1)□, V = 3253.8(5) Å3, Z = 1, with final residuals R1 = 0.0508, wR2 = 0.1356。 The compounds M2(dppap)(M = Cr, 4; Mo, 5) were prepared by reaction of CrCl2 and Mo2(O2CCH3)4, respectively, with lithium salt of Hdppap (Hdppap = 2-(diphenylphosphinoamino)pyridine) in THF. The complex Mo2O2(dppap)4, 6, was prepared by dissolving complex 5 in THF, and layered with hexanes in air. Reaction of [Cu(CH3CN)4][PF6] with Hdppap in CH2Cl2 afforded the complex [Cu(HDppap)2][PF6], 7. These compounds have been characterized by analytical and spectroscopic data. The structures of 4, 6 and 7 have been determined by X-ray crystallography. Crystal data for 4 : space group Pī, a = 10.321(1) Å, b = 11.991(1) Å, c = 13.813(1) Å, α = 101.235(1) □, □ = 99.821(1) □, γ = 94.478(1) □, V = 1641.0(2) Å3, Z = 1, with final residuals R1 = 0.0522, wR2 = 0.1399. The Cr-Cr distance is 1.8866(9) Å which indicates a supershort quadruple bond. Crystal data for 6 : space group C2/c, a = 21.117(1) Å, b =17.617(1) Å, c = 20.435(1) Å, β = 93.595(1)□, V = 7587.4(7) Å3, Z = 4, with final residuals R1 = 0.0480, wR2 = 0.1089. Crystal data for 7 : space group C2, a = 15.653(1) Å, b = 11.883(1), c = 12.335(1) Å, □ = 121.578(6) □, V = 1954.6(3) Å3, Z = 2, with final residuals R1 = 0.0491，wR2 = 0.1413.