制备了双(3,5-二叔丁基-2-苯酚)胺([ONO] H 3)的同构钒,铌和钽配合物,并进行了表征,以评估金属离子对金属氧化还原活性的影响。配体平台。制备了具有通式[ONO] MCl 2 L(M = V,L = THF,1-V ; M = Nb,L = Et 2 O,1-Nb)的新钒和铌配合物,并通过X进行结构分析射线晶体学。固态结构表明,铌衍生物与钽类似物1-Ta在电子上相似,其包含还原的(ONO)配体和铌(V)金属离子,[ONO cat ] Nb VCl 2(OEt 2);钒衍生物最好描述为钒(IV)络合物[ONO sq ] V IV Cl 2(THF)。在所有三种金属络合物上进行单电子氧化,得到[ONO] MCl 3衍生物(3-V,3-Nb,3-Ta)。对于所有三种衍生物,氧化发生在(ONO)配体上。在铌和钽的情况下,获得了表征为[ONO sq ] M V Cl 3的电子相似的配合物
Reactivity of Diazoalkanes with Tantalum(V) Complexes of a Tridentate Amido-Bis(phenolate) Ligand
作者:Ryan A. Zarkesh、Alan F. Heyduk
DOI:10.1021/om900701n
日期:2009.12.14
While a dimethyltantalum(V) complex of the [ONOcat]3− ligand ([ONOcat]H3 = N,N-bis(3,5-di-tert-butyl-2-phenol)amine) reacted with diazoalkane to afford products of insertion into the Ta−Me bond, the dichlorotantalum(V) complex [ONOcat]TaCl2(OEt2) reacted with 2 equiv of Ph2CN2 to form the ketazine adduct [ONOcat]TaCl2(η2(N,N′)-Ph2C═NN═CPh2). When Ph2CN2 was added to the dichloride in neat styrene,