Scandium and yttrium complexes of the diamide–diamine donor ligand (2-C5H4N)CH2N(CH2CH2NSiMe3)2: chloride, primary and secondary amide, benzamidinate and alkyl functionalised derivatives
作者:Michael E. G. Skinner、Philip Mountford
DOI:10.1039/b111469g
日期:2002.4.9
Five- and six-coordinate scandium and yttrium complexes of the recently described diamideâdiamine donor ligand N2NNâ² (where H2N2NNâ²
= (2-C5H4N)CH2NCH2CH2N(H)SiMe3}2) are described. Reaction of ScCl3 with Li2N2NNâ² gave five-coordinate [ScCl(N2NNâ²)] 1 in excellent yield. The corresponding reaction with YCl3 in tetrahydrofuran (thf) or pyridine (py) solution afforded âateâ complexes best described as [YCl(N2NNâ²)(L)]·1.5(LiCl) (L = thf 2 or py 3). The two chloride complexes 1 and 2 are useful starting materials for primary
and secondary amide, benzamidinate and alkyl complexes of Sc and Y supported by the N2NNⲠligand. Thus reaction of 1 or 2 with LiN(SiMe3)2·Et2O, LiNMe2 or LiNHR (R =
tBu or Ar, where Ar = 2,6-C6H3iPr2) gave the corresponding five-coordinate amide derivatives [M(NRRâ³)(N2NNâ²)] (M = Sc, R = Râ³
= SiMe34 or Me 6, or R = H, Râ³
=
tBu 8 or Ar 9; M = Y, R = Râ³
= SiMe35, or R = H, Râ³
= Ar 10).
The crystal structure of 5 is described. The Ï-bond metathesis reaction of [Sc(NMe2)(N2NNâ²)] 6 with ArFNH2 (ArF
= C6F5) gave the corresponding primary flurophenylamide derivative 7. The reaction of 1 or 2 with Li[PhC(NSiMe3)2] gave the fluxional, six-coordinate benzamidinate derivatives [MPhC(NSiMe3)2}(N2NNâ²)] (M = Sc 11 or Y 12), the crystal structures of which are reported. Finally, reaction of 1 with LiCH2SiMe3 formed the alkyl derivative [Sc(CH2SiMe3)(N2NNâ²)] 13 in reasonable yield; the crystal structure of 13 is described.
最近报道的二酰胺-二胺供体配体N2NN'(其中H2N2NN' = (2-C5H4N)CH2NCH2CH2N(H)SiMe3}2)的五配位和六配位钪和钇配合物。将ScCl3与Li2N2NN'反应得到了高产率的五配位[ScCl(N2NN')] 1。在四氢呋喃(thf)或吡啶(py)溶液中,将YCl3与Li2N2NN'反应得到了最佳描述为[YCl(N2NN')(L)]·1.5(LiCl)的“ate”配合物(L = thf 2或py 3)。两种氯配合物1和2是制备由N2NN'配体支撑的Sc和Y的一级和二级酰胺、苯甲酰亚胺和烷基配合物的重要起始材料。因此,将1或2与LiN(SiMe3)2·Et2O、LiNMe2或LiNHR(R = tBu或Ar,其中Ar = 2,6-C6H3iPr2)反应得到了相应的五配位酰胺衍生物[M(NRR')(N2NN')](M = Sc,R = R' = SiMe34或Me 6,或R = H,R' = tBu 8或Ar 9;M = Y,R = R' = SiMe35,或R = H,R' = Ar 10)。描述了5的晶体结构。[Sc(NMe2)(N2NN')] 6与ArFNH2(ArF = C6F5)的Ï-键置换反应得到了相应的一级氟苯甲酰胺衍生物7。将1或2与Li[PhC(NSiMe3)2]反应得到了动态的六配位苯甲酰亚胺衍生物[MPhC(NSiMe3)2}(N2NN')](M = Sc 11或Y 12),报告了其晶体结构。最后,将1与LiCH2SiMe3反应形成了合理的产率的烷基衍生物[Sc(CH2SiMe3)(N2NN')] 13;描述了13的晶体结构。