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Synthesis of molybdenum(VI) monoimido alkyl and alkylidene complexes

机译：钼（VI）单亚氨基烷基和亚烷基络合物的合成

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In this paper we report the synthesis of several new Mo(NR)Cl-4(THF) species (R = C6F5, 3,5-(CF3)(2)C6H3, 1-adamantyl, CPh3, and 2,6-i-Pr2C6H3 via the treatment Of MoCl4(THF)(2) with azides and their reactions with neopentyl reagents. Addition of Mo(NR)Cl-4(THF) complexes in toluene to a cold solution of NpMgCl in ether gave Mo(NR)Np3Cl species (R = C6F5,3,5-(CF3)(2)C6H3, Ad, Ph3C, and 2,6-i-Pr2C6H3 (Ar); Np = CH2-t-Bu) in poor (35%) to modest (51%) yields. Heating Mo(NAr)Np3Cl in C6D6 to 50 degrees C results in a.-hydrogen abstraction to give neopentane and a molecule whose NMR spectra are consistent with it being Mo(NAr)(CH-t-Bu)(CH2-t-Bu)Cl; it decomposed bimolecularly upon attempted isolation. The other Mo(NR)Np3Cl species were found to be more stable than Mo(NAr)Np3Cl, but when they did decompose at elevated temperatures, no neopentylidene complex could be observed. Addition of neopentyllithium to Mo(NR)Np3Cl species (R = Ar, CPh3, or Ad) yielded Mo(NR)(CH-t-Bu)Np-2 species, the adamantylimido version of which is unstable toward bimolecular decomposition. Addition of neopentyllithium to Mo(NR)Np3Cl complexes in which R = pentafluorophenyl or 3,5-trifluoromethylphenyl led to intractable mixtures. Addition of 1 equiv of 2,6-diisopropylphenol, 2,6-dimethylphenol, or 3,5-(2,4,6-i-Pr3C6H2)(2)C6H3OH (HIPTOH) to Mo(NCPh3)(CH-t-Bu)Np-2 led to formation of Mo(NCPh3)(CH-t-Bu)Np(OR) species, while treatment of Mo(NCPh3)(CH-t-BU)(2)(CH2-t-Bu) with C6F5OH gave Mo(NCPh3)Np-3(OC6F5). The three monophenoxide neopentylidene complexes showed poor to moderate metathesis activity for ring-closing a small selection of substrates. X-ray studies were completed for Mo[N-3,5-(CF3)(2)C6H3]Cl-4(THF), Mo[N-3,5-(CF3)(2)C6H3]Np3Cl, Mo(NCPh3)Np3Cl, and Mo(NCPh3)(CH-t-Bu)(CH2-t-Bu)(OHIPT).
机译：在本文中，我们报告了几种新的Mo（NR）Cl-4（THF）物种的合成（R = C6F5、3,5-（CF3）（2）C6H3、1-金刚烷基，CPh3和2,6-i -通过叠氮化物处理MoCl4（THF）（2）及其与新戊基试剂的反应生成Pr2C6H3将甲苯中的Mo（NR）Cl-4（THF）络合物加到NpMgCl的乙醚冷溶液中，得到Mo（NR） Np3Cl物种（R = C6F5,3,5-（CF3）（2）C6H3，Ad，Ph3C和2,6-i-Pr2C6H3（Ar）; Np = CH2-t-Bu）在较差的（35％）中适度（51％）的产率。将C6D6中的Mo（NAr）Np3Cl加热到50摄氏度会导致氢脱氢生成新戊烷，并且其NMR光谱与Mo（NAr）（CH-t-Bu）一致）（CH2-t-Bu）Cl;尝试分离时会双分子分解。其他Mo（NR）Np3Cl种类比Mo（NAr）Np3Cl稳定，但当它们在高温下分解时，没有新戊二烯络合物向Mo（NR）Np3Cl物种（R = Ar，CPh3或Ad）中添加新戊基锂产生Mo（NR）（CH-t-Bu）Np-2物种，其达曼替林多版本对双分子分解不稳定。将新戊基锂加到Mo（NR）Np3Cl络合物中，其中R =五氟苯基或3,5-三氟甲基苯基，导致形成难处理的混合物。将1当量的2,6-二异丙基苯酚，2,6-二甲基苯酚或3,5-（2,4,6-i-Pr3C6H2）（2）C6H3OH（HIPTOH）加至Mo（NCPh3）（CH-t- Bu）Np-2导致形成Mo（NCPh3）（CH-t-Bu）Np（OR）物种，同时处理Mo（NCPh3）（CH-t-BU）（2）（CH2-t-Bu）用C6F5OH得到Mo（NCPh3）Np-3（OC6F5）。三种单酚盐新亚戊二烯配合物显示出较弱至中等的复分解活性，可封闭少量底物。 Mo [N-3,5-（CF3）（2）C6H3] Cl-4（THF），Mo [N-3,5-（CF3）（2）C6H3] Np3Cl，Mo（ NCPh3）Np3Cl和Mo（NCPh3）（CH-t-Bu）（CH2-t-Bu）（OHIPT）。

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