Cross Warren B, Anderson James C, Wilson Claire, Blake Alexander J
School of Chemistry, University of Nottingham, Nottingham NG7 2RD, UK.
Inorg Chem. 2006 May 29;45(11):4556-61. doi: 10.1021/ic0521269.
The novel 16-electron molybdenum oxo-imido bis(aryloxide) complexes [Mo(NtBu)(O)(2,6-Me2C6H3O)2(py)] (1) and [Mo(NtBu)(O)(2,6-iPr2C6H3O)2(py)] (2) have been prepared by the salt elimination reactions of [Mo(NtBu)(O)Cl2(DME)] with the appropriate lithium aryloxide and from the cycloaddition reactions of tert-butyl isocyanate with the appropriate molybdenum dioxo bis(aryloxide) complex [Mo(O)2(OAr)2(py)n]. Complexes 1 and 2 are the first isolable and crystallographically characterized molybdenum oxo-imido aryloxide complexes. The geometry around the metal in complexes 1 and 2 is best described as a distorted trigonal bipyramid, with the imido and pyridine ligands occupying the axial positions and the oxo and aryloxide ligands in the equatorial plane. X-ray and IR data have confirmed that the imido ligand is the dominant pi donor in the complexes, resulting in an Mo-O bond order of less than 2.5. Reaction of [Mo(NtBu)(O)Cl2(DME)] with Li(OCH2tBu) instead gave the novel complex [Mo(NtBu)(OCH2tBu)3Cl(py)] (3).
新型的16电子钼氧-亚氨基双（芳氧基）配合物[Mo(NtBu)(O)(2,6-Me2C6H3O)2(py)]（1）和[Mo(NtBu)(O)(2,6-iPr2C6H3O)2(py)]（2）通过[Mo(NtBu)(O)Cl2(DME)]与适当的芳氧基锂的盐消除反应以及叔丁基异氰酸酯与适当的二氧钼双（芳氧基）配合物[Mo(O)2(OAr)2(py)n]的环加成反应制备而成。配合物1和2是首批可分离且经晶体学表征的钼氧-亚氨基芳氧基配合物。配合物1和2中金属周围的几何构型最好描述为扭曲的三角双锥，亚氨基和吡啶配体占据轴向位置，氧和芳氧基配体在赤道平面。X射线和红外数据证实，亚氨基配体是配合物中的主要π供体，导致Mo-O键级小于2.5。[Mo(NtBu)(O)Cl2(DME)]与Li(OCH2tBu)反应则得到新型配合物[Mo(NtBu)(OCH2tBu)3Cl(py)]（3）。
