Macrocyclic hydroperoxocobalt(III) complex: Photochemistry, spectroscopy, and crystal structure
Macrocyclic hydroperoxocobalt(III) complex: Photochemistry, spectroscopy, and crystal structure
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DOI：
10.1021/ic001391l
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发表时间：
2001-05-07
影响因子：
4.6
通讯作者：
Bakac, A
中科院分区：
文献类型：
--
作者：
Guzei, IA;Bakac, A
氢过氧钴配合物[L-2（CH_3CN）CoOOH]（ClO_4）（2）. CH 3CN（L-2 = meso-5，7，7，12，14，14-Me-6-[14]aneN（4））在晶格中以离散的阴离子、阳离子和溶剂化乙腈分子结晶。该配合物的晶体结构为单斜晶系，空间群为P2（1）/n，a = 10.4230（5）埃，B = 16.1561（8）埃，c = 17.4676（9）埃，β = 92.267（1）度，V = 2939.2（3）埃（3），Z = 4。O-O键长为1.397（4）埃，O（2）-O（1）-Co角跨度为117.7度。红外光谱中的O-O伸缩出现在815 cm（-1）处。L-2（H2O）CoOOH 2+的酸性水溶液在355-和266-nm处发生光解，导致Co-O键的均裂，产生L2 Co（H2O）（2）（2+）和HO 2。O-2（.-）作为唯一的产品。这两种碎片在O2和C（NO2）的单独实验中被选择性地清除（4）。没有光化学O-O键均裂的证据，大概是因为适当的光学跃迁被HO 2-Co LMCT跃迁所掩盖。
The hydroperoxocobalt complex [L-2(CH3CN)CoOOH](ClO4)(2). CH3CN (L-2 = meso-5,7,7,12,14,14-Me-6-[14]aneN(4)) crystallizes with discrete anions, cations, and solvate acetonitrile molecules in the lattice. The complex crystallizes in the monoclinic space group P2(1)/n, a = 10.4230(5) Angstrom, b = 16.1561(8) Angstrom, c = 17.4676(9) Angstrom, beta = 92.267(1)degrees, V = 2939.2(3) Angstrom (3), Z = 4. The O-O bond length is 1.397(4) Angstrom, and the O(2)-O(1)-Co angle spans 117.7 degrees. The O-O stretch in the infrared spectrum appears at 815 cm(-1). The 355- and 266-nm photolysis of acidic aqueous solutions of L-2(H2O)CoOOH2+ results in homolytic splitting of the Co-O bond and yields L2Co(H2O)(2)(2+) and HO2./O-2(.-) as the only products. The two fragments were scavenged selectively in separate experiments with Oz and C(NO2)(4). There is no evidence for photochemical O-O bond homolysis, presumably because the appropriate optical transition is masked by the HO2-to-Co LMCT transition.