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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and characterization of molybdenum oxo complexes of two tripodal ligands:reactivity studies of a functional model for molybdenum oxotransferases
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Synthesis and characterization of molybdenum oxo complexes of two tripodal ligands:reactivity studies of a functional model for molybdenum oxotransferases

机译：两个三脚架配体的钼氧代配合物的合成与表征：钼氧代转移酶功能模型的反应性研究

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摘要

Reaction of the tetradentate ligand N-(2-hydroxybenzyl)-N,N-bis(2-pyridylmethyl)amine (L-OH) with MoO_2Cl_2 in methanol in the presence of NaOMe and PF_6~- results in the formation of [MoO_2(L-O)]PF_6.Similarly,the reaction of N-(2-mercaptobenzyl)-N,N-bis(2-pyridylmethyl)amine (L-SH) with MoO_2(acac)_2 leads to the formation of [MoO_2(L-S)]~+.The dioxo-molybdenum complex [MoO_2(L-O)]~+ reacts with phosphines in methanol to afford phosphine oxides and an air-sensitive molybdenum complex,tentatively identified as [Mo(IV)O(L-O)(OCH_3)].The latter complex is capable of reducing biological oxygen donors such as DMSO or nitrate,thereby mimicking the activity of DMSO reductase and nitrate reductase.Reaction of [MoO_2(L-O)]PF_6 with PPh_3 in other solvents than methanol leads to the formation of the Mo(v) dimer [(L-O)OMo(mu-O)MoO(L-O)](PF_6)_2.The crystal structures of [MoO_2(L-O)]PF_6 and the mu-oxo bridged dimer are presented.
机译：在NaOMe和PF_6〜-存在下，四齿配体N-（2-羟基苄基）-N，N-双（2-吡啶基甲基）胺（L-OH）与MoO_2Cl_2在甲醇中的反应导致形成[MoO_2（（ LO）] PF_6。类似地，N-（2-巯基苄基）-N，N-双（2-吡啶基甲基）胺（L-SH）与MoO_2（acac）_2的反应导致[MoO_2（LS）的形成]〜+。二氧钼配合物[MoO_2（LO）]〜+在甲醇中与膦反应生成氧化膦和对空气敏感的钼配合物，暂定为[Mo（IV）O（LO）（OCH_3）]。后者的复合物能够还原DMSO或硝酸盐等生物供氧体，从而模仿DMSO还原酶和硝酸盐还原酶的活性。[MoO_2（LO）] PF_6与PPh_3在甲醇以外的其他溶剂中的反应导致形成Mo（v）二聚体[（LO）OMo（mu-O）MoO（LO）]（PF_6）_2。给出了[MoO_2（LO）] PF_6和mu-oxo桥联二聚体的晶体结构。

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