SYNTHESES, PROPERTIES, AND ELECTROCHEMISTRY OF TRANSITION-METAL COMPLEXES OF THE MACROCYCLE 1,4,7-TRIS(2-PYRIDYLMETHYL)-1,4,7-TRIAZACYCLONONANE (L) - CRYSTAL-STRUCTURES OF [NIL](CLO4)2, [MNL](CLO4)2, AND [PDL](PF6)2 CONTAINING A DISTORTED-SQUARE-BASE-PYRAMIDAL PDIIN5 CORE
SYNTHESES, PROPERTIES, AND ELECTROCHEMISTRY OF TRANSITION-METAL COMPLEXES OF THE MACROCYCLE 1,4,7-TRIS(2-PYRIDYLMETHYL)-1,4,7-TRIAZACYCLONONANE (L) - CRYSTAL-STRUCTURES OF [NIL](CLO4)2, [MNL](CLO4)2, AND [PDL](PF6)2 CONTAINING A DISTORTED-SQUARE-BASE-PYRAMIDAL PDIIN5 CORE
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DOI：
10.1021/ic00247a020
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发表时间：
1986-12-31
影响因子：
4.6
通讯作者：
WEISS, J
中科院分区：
文献类型：
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作者：
WIEGHARDT, K;SCHOFFMANN, E;WEISS, J
Mn（II）、Fe（II）、Co（II）、Ni（II）、Cu（II））在添加NaClO 4-H2O时产生相应的络合物[LM]（ClO 4）2。用30%H2O2氧化[CoL]（C104）2和[FeL]（C104）2产生配合物[LM]（C104）3（M= Co（III），Fe（III））。[LRu]2+/3+和[LCr] 3+配合物也制备为PF 6 '盐。乙酸钯（II）与L在甲醇中反应产生红色[LPd] 2+，其以PF 6 ~盐形式分离。[MnL]（C104）2（1）和[NiL]（C104）2（2）的晶体结构表明，前者金属离子处于六氮供体的扭曲棱柱环境，后者处于扭曲八面体环境。对于化合物1，晶体为单斜晶系（P2，/c），其中a= 8.478（3）A，B= 17.050（4）A，c= 20.247（6）A，λ = 101.52（2），V= 2867.7（12）A 3，并且Z= 4。化合物2形成三角晶体（R3），其中a= 17.155（3）A，c= 7.892（2）A，V= 2011（1）A3，并且Z= 3。[LPd]（PF 6）2（3）的晶体为三斜晶系（Pi），a= 9.060（4）A，B= 10.372（4）A，c= 17.683（6）A，a= 102.44（3），λ = 92.28（3），y= 112.01（3），V= 1491（2）A 3，Z= 2。在[LPd] 2+中，配体为五齿配体，有一个吡啶甲基臂，钯中心周围的几何构型为扭曲的正方形，平均赤道Pd-N键距为2.035 A，轴向Pd-N键距为2.580（3）A。[LM]（C_（104））_2（M= Mn，Fe，Co，Ni）配合物在乙腈中的循环伏安图显示出可逆或准可逆的单电子转移过程。报道了所有配合物的氧化还原电位和电子光谱。
Mn (II), Fe (II), Co (II), Ni (II), Cu (II)) yielded upon addition of NaC104-H20 the corresponding complexes [LM](C104) 2. Oxidation of [CoL](C104) 2 and [FeL](C104) 2 with 30% H202 yielded the complexes [LM](C104) 3 (M= Co (III), Fe (III)).[LRu] 2+/3+ and [LCr] 3+ complexes were also prepared as PF6" salts. The reaction of palladium (II) acetate with L in methanol yielded red [LPd] 2+, which was isolated as a PF6~ salt. The crystal structures of [MnL](C104) 2 (1) and of [NiL](C104) 2 (2) show the metal ions to be in a distorted-prismatic environment of six nitrogen donors for the former and in a distorted-octahedral environment for the latter. For compound 1 the crystals are monoclinic (P2,/c) with a= 8.478 (3) A, b= 17.050 (4) A, c= 20.247 (6) A, ß= 101.52 (2), V= 2867.7 (12) A3, and Z= 4. Compound 2 forms trigonal crystals (R3) with a= 17.155 (3) A, c= 7.892 (2) A, V= 2011 (1) A3, and Z= 3. Crystals of [LPd](PF6) 2 (3) are triclinic (Pi) with a= 9.060 (4) A, b= 10.372 (4) A, c= 17.683 (6) A, a= 102.44 (3), ß= 92.28 (3), y= 112.01 (3), V= 1491 (2) A3, and Z= 2. In [LPd] 2+ the ligand is pentadentate with one dangling pyridylmethyl arm and the geometry around the palladium center is distorted square base pyramidalwith an averaged equatorial Pd-N bond distance of 2.035 A and an axial Pd-N distance of 2.580 (3) A. The cyclic voltammograms of [LM](C104) 2 (M= Mn, Fe, Co, Ni) complexes in acetonitrile show a reversible or quasi-reversible one-electron-transfer process. The redox potentials and electronic spectra of all complexes are reported.