The isopropylation of biphenyl (BP) was examined over transition metal substituted aluminophosphates (MAPO-5; M: Co and Ni) with 12-membered (12-MR) oxygen ring pore-entrances of AFI topology. The MAPO-5 samples were synthesized by dry gel conversion method using trimethylamine as a structure directing agent, and their properties were characterized by XRD, XPS, SEM, N₂ adsorption, NH₃-TPD, pyridine adsorption, and o-xylene uptake. They are clear crystals without impurity phases and agglomerates, and found small amounts of Brønsted acid sites which are expecting active for acid catalysis. The isopropylation of BP over both of Co(5)APO-5 and Ni(5)APO-5 at 250 °C gave the high selectivities for 4,4′-DIPB: 65–75%. 4-IPBP is almost exclusive precursor of 4,4′- and 3,4′-DIPB. 3-IPBP was not significantly concerned even though 3-IPBP was predominant among IPBP isomers at the late stages: the MAPO-5 channels allow preferential access of 4-IPBP, and prevent the access of 3-IPBP due to reactant selectivity mechanism. The selective formation of 4,4′-DIPB occurred by preferential exclusion of bulkier 3,4′-DIPB and other isomers through the steric interaction of transition states with the channels by the restricted transition state selectivity mechanism. MAPO-5 (M: Co and Ni) has the same level of the selectivities for 4,4′-DIPB to SSZ-24 and other MAPO-5 (M: Si, Mg, and Zn), and these selectivities were originated by the AFI channels. The selectivities for 4,4′-DIPB were kept 65–75% at low and moderate temperatures over MAPO-5 (M: Co and Ni); however, they were decreased by the isomerization to stable 3,4′-DIPB with the increase in temperature.

中文翻译：

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联苯在过渡金属取代的磷酸铝上的异丙基化：MAPO-5（M：Co和Ni）

在具有AFI拓扑结构的12元（12-MR）氧环孔入口的过渡金属取代的磷酸铝盐（MAPO-5; M：Co和Ni）上检查了联苯（BP）的异丙基化。以三甲胺为结构导向剂，通过干凝胶转化法合成了MAPO-5样品，并通过XRD，XPS，SEM，N ₂吸附，NH ₃ -TPD，吡啶吸附和邻位表征了其性质。-二甲苯吸收。它们是透明的晶体，没有杂质相和附聚物，并且发现了少量的布朗斯台德酸位点，这些位点有望对酸催化起作用。在250°C时BP在Co（5）APO-5和Ni（5）APO-5上的异丙基化使4,4'-DIPB的选择性高：65-75％。4-IPBP几乎是4,4'-和3,4'-DIPB的专有前体。尽管3-IPBP在后期的IPBP异构体中占主导地位，但3-IPBP并未受到太大关注：MAPO-5通道允许4-IPBP优先进入，并由于反应物选择性机制而阻止3-IPBP进入。通过受限的过渡态选择性机制，通过过渡态与通道的空间相互作用，优先排除体积较大的3,4'-DIPB和其他异构体，从而实现了4,4'-DIPB的选择性形成。MAPO-5（M：Co和Ni）对4,4'-DIPB对SSZ-24和其他MAPO-5（M：Si，Mg和Zn）的选择性水平相同，这些选择性是由AFI通道产生的。在MAPO-5（M：Co和Ni）的低温和中温下，对4,4'-DIPB的选择性保持在65–75％。然而，随着温度的升高，它们被异构化降低为稳定的3,4'-DIPB。