Hitchcock Peter B, Khvostov Alexei V, Lappert Michael F, Protchenko Andrey V
The Chemistry Department, University of Sussex, Brighton, U.K.BN1 9QJ.
Dalton Trans. 2009 Apr 7(13):2383-91. doi: 10.1039/b818969b. Epub 2009 Feb 10.
Heteroleptic beta-diketiminatoytterbium(ii) complexes [{Yb(L)(mu-I)(thf)}(2)] [: L = {N(Ar*)C(Me)}(2)CH = L(1), : L = {N(SiMe(3))C(Ph)}(2)CH = L(2); Ar* = C(6)H(3)(i)Pr(2)-2,6] were prepared by a salt elimination [from YbI(2)(thf)(2) and KL] or by a ligand redistribution [from YbI(2)(thf)(2) and YbL(2)] reaction. Complexes and were convenient precursors to some new Yb(ii) heteroleptic compounds. Thus, reaction of and with KN(SiMe(3))(2) yielded the mononuclear amido compounds [Yb(L){N(SiMe(3))(2)}(thf)] (: L = L(1) and : L = L(2)). Similarly, with K{N(H)Ar*} gave [Yb(L(1)){N(H)Ar*}(thf)] (). Complex was also obtained via a protolytic reaction of [Yb{N(SiMe(3))(2)}(2)(thf)(2)] with HL(1) at an elevated temperature. Treatment of with slightly less than a stoichiometric amount of K{CH(SiMe(3))(2)} afforded [Yb(L(1)){CH(SiMe(3))(2)}(thf)] (), while using even a small excess of the alkyl reagent resulted in the deprotonation of the beta-diketiminato ligand and the formation of the known dimer [{Yb(L(3))(thf)}(2)] [, L(3) = Ncombining macronC(Me)C(H)C(C[combining macron]H(2))N(Ar*)]. Compounds or reacted with KCPh(3) in thf yielding [Yb(L(1)){eta(5)-C(6)H(5)CPh(2)}(thf)] () or [Yb(CPh(3))(2)(thf)(2)] (), respectively; the latter has two differently coordinated CPh(3) ligands. The molecular structures of 1, 2, 4, 5, 6, 8 and 9 were determined by X-ray diffraction.
通过盐消除反应(由YbI₂(thf)₂和KL反应)或配体再分配反应(由YbI₂(thf)₂和YbL₂反应)制备了杂配β-二酮亚胺基镱(II)配合物[{Yb(L)(μ-I)(thf)}₂] [其中:L = {N(Ar*)C(Me)}₂CH = L₁,其中:L = {N(SiMe₃)C(Ph)}₂CH = L₂;Ar* = C₆H₃(iPr)₂-2,6]。配合物1和2是一些新型Yb(II)杂配化合物的便利前体。因此,1和2与KN(SiMe₃)₂反应生成单核氨基化合物[Yb(L){N(SiMe₃)₂}(thf)] [其中:L = L₁,其中:L = L₂]。类似地,2与K{N(H)Ar*}反应得到[Yb(L₁){N(H)Ar*}(thf)](3)。配合物4也通过[Yb{N(SiMe₃)₂}₂(thf)₂]与HL₁在高温下的质子解反应获得。用略少于化学计量的K{CH(SiMe₃)₂}处理2得到[Yb(L₁){CH(SiMe₃)₂}(thf)](5),而即使使用少量过量的烷基试剂也会导致β-二酮亚胺基配体去质子化并形成已知的二聚体[{Yb(L₃)(thf)}₂] [其中,L₃ = N上加横线C(Me)C(H)C(上加横线H₂)N(Ar*)]。化合物1或2在thf中与KCPh₃反应分别生成[Yb(L₁){η⁵-C₆H₅CPh₂}(thf)](6)或[Yb(CPh₃)₂(thf)₂](7);后者有两个配位方式不同的CPh₃配体。通过X射线衍射确定了1、2、4、5、6、8和9的分子结构。