HIGHLY OXIDATION RESISTANT INORGANIC-PORPHYRIN ANALOG POLYOXOMETALATE OXIDATION CATALYSTS .1. THE SYNTHESIS AND CHARACTERIZATION OF AQUEOUS-SOLUBLE POTASSIUM-SALTS OF ALPHA-2-P2W17O61(MN+.OH2)(N-10) AND ORGANIC-SOLVENT SOLUBLE TETRA-NORMAL-BUTYLAMMONIUM SALTS OF ALPHA-2-P2W17O61(MN+.BR)(N-11) (M = MN3+, FE3+, CO2+, NI2+, CU2+)
HIGHLY OXIDATION RESISTANT INORGANIC-PORPHYRIN ANALOG POLYOXOMETALATE OXIDATION CATALYSTS .1. THE SYNTHESIS AND CHARACTERIZATION OF AQUEOUS-SOLUBLE POTASSIUM-SALTS OF ALPHA-2-P2W17O61(MN+.OH2)(N-10) AND ORGANIC-SOLVENT SOLUBLE TETRA-NORMAL-BUTYLAMMONIUM SALTS OF ALPHA-2-P2W17O61(MN+.BR)(N-11) (M = MN3+, FE3+, CO2+, NI2+, CU2+)
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DOI：
10.1021/ja00019a018
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发表时间：
1991-09-11
影响因子：
15
通讯作者：
FINKE, RG
中科院分区：
文献类型：
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作者：
LYON, DK;MILLER, WK;FINKE, RG
本文报道了水溶性钾盐（L = H_2O）和有机溶性四正丁基铵盐（L = Br ~-）的异构体α_2-P_2W_（17）O_（61）（Mn ~+·L）y-（Mn ~+ = Mn ~（3+）、Fe ~（3+）、Co ~（2+）、Ni ~（2+）和Cu ~（2+））的合成和表征。 这些配合物的特征在于P-31 NMR，元素分析，沉降平衡分子量，热重分析（TGA），温度变化的固态磁化率的研究，紫外-可见光谱，红外光谱（IR），和W-183 NMR。 这些化合物构成了第一个分离的单取代的Dawson α-2-异构体络合物，其已经制备成不含α-1-异构体。 初步的轴向碱结合的α-2-[（n-C4 H9）4 N]7.3H0.7P2W17O61（Mn.Br）的研究报告，并证明，周围的过渡金属的“口袋”实际上是有点阻碍，但不如空间拥挤的卟啉。 进一步的研究表明，α-2-[（n-C4 H9）4 N]7.3H0.7P2W17O61（Mn·Br）即使在48小时内也不会被1500当量的PhIO氧化降解。 在随附的论文中，报道了通过α-2-P2 W17 O 61（M.L）y-的氧化催化，产生烯烃环氧化和脂肪族和芳香族羟基化。
The synthesis and characterization of isolated, isomerically pure alpha-2-P2W17O61(Mn+.L)y- (Mn+ = Mn3+, Fe3+, Co2+, Ni2+, and Cu2+) as aqueous-soluble potassium salts (L = H2O) and organic-soluble tetra-n-butylammonium salts (L = Br-) are reported. These complexes have been characterized by P-31 NMR, elemental analysis, sedimentation equilibrium molecular weight, thermal gravimetric analysis (TGA), temperature-varied solid-state magnetic susceptibility studies, UV-visible spectroscopy, infrared spectroscopy (IR), and W-183 NMR. These compounds constitute the first isolated monosubstituted Dawson alpha-2-isomer complexes that have been prepared free of the alpha-1-isomer. Preliminary axial-base binding studies for alpha-2-[(n-C4H9)4N]7.3H0.7P2W17O61(Mn.Br) are reported and demonstrate that the ''pocket'' around the transition metal is actually somewhat hindered, but less so than in sterically congested porphyrins. Further studies show that alpha-2-[(n-C4H9)4N]7.3H0.7P2W17O61(Mn.Br) is not oxidatively degraded by 1500 equiv of PhIO even over 48 h. In an accompanying paper, oxidation catalysis by alpha-2-P2W17O61(M.L)y- is reported yielding olefin epoxidations and aliphatic and aromatic hydroxylations.