Synthesis and structures of some heterometallic [(Li, Y)(2), (M-3, Ce) (M = Li or Na), (Li, Zr-2) and (Li, Zr)(4)] oligomeric diamides derived from 1,2-bis(neopentylamino)benzene

摘要

The following crystalline, X-ray-characterised heterometallic oligomeric diamides have been prepared in good yield under mild conditions in diethyl ether from the dilithio or disodio derivative of the N, N'-dineopentyl-1,2-diaminobenzene [{N(H)(CH2But)}(2)C6H4-1,2] (abbreviated as H2L): [Y(L)(mu-Cl)(2)Li(OEt2)(2)](2) (1), [Li(OEt2)(2)Li(mu(2)-Cl)(4)(mu(3)-Cl)(2){Zr(L)}(2)](2) (2), [Zr(L)(2)(mu-Cl)-{ Li(OEt2)(2)}(mu(2)-Cl)(2)Zr(L)](3), [Ce{mu-L)M}(3)(OEt2)(1/2)] (3M = Li1.82Na1.18) (4), [Ce{(mu-L)Na}(3)(OEt2)] (5) and [Ce{(mu-L)Na}(3)] (6). Compounds 1 - 3 were obtained from Li-2(L) andYCl(3) (the colourless 1) or ZrCl4 (the red 2 and 3), while the red 4 and 5 were isolated from CeCl3 and M-2(L) (3M= Li1.82Na1.18) (4) or Na-2(L) (5). Attempted oxidation of 5 with Br-2 in hexane yielded the black 6. The ligand L is N, N'-chelating to each of the d- or f-block metals in 1-6; and in 4-6 L is also acting as a bridge between Ce and the alkali metal, to which L is thus also chelating.