Department of Chemistry and Biochemistry, University of Sussex, Brighton, UK BN1 9QJ.
Dalton Trans. 2010 Jul 28;39(28):6426-33. doi: 10.1039/c0dt00071j. Epub 2010 Jun 21.
The new [Al(L(Tol))Br(2)] (1) and the known [Al(L(Ph))Me(2)] (2) were prepared as potential precursors to more novel aluminium compounds. In the event, only the latter was effective. Thus 2 and two equivalents of potassium was the source of [{Al(L(Ph))Me(2)K(2)(OEt(2))}(2)] (3). The complexes [{KSm(L(Ph))(2)}(2)] (4), [Sm(2)(L(Dph))(3)] (5) and [Sm(L(Tol,Ad))(L(Tol,Ad)-H)] (6) were obtained from SmI(2) and two equivalents of the appropriate potassium beta-diketiminate [L(Ph) or L(Tol) or L(Dph) = {N(SiMe(3))C(Ar)}(2)CH, Ar = Ph or C(6)H(4)Me-4 or C(6)H(4)Ph-4; L(Tol,Ad) = N(SiMe(3))C(C(6)H(4)Me-4)C(H)C(Ad)NSiMe(3), L(Tol,Ad)-H = N(SiMe(3))C(C(6)H(4)Me-4)C(H)C(Ad)NSiMe(2)CH(2), Ad = 1-adamantyl]. Crystalline complexes 3-6 were isolated in very low (4, 5) or satisfactory (3, 6) yield and characterised by X-ray diffraction. From comparisons of the M-N, N-C, C-C and C-C(Ar) bond lengths with suitable standards, complexes 3-5 are assigned as containing Al(3+)/(L(Ph))(3-) for 3, Sm(3+)/(L(Ph))(-)/(L(Ph))(3-) for 4, and {Sm(3+)}(2)/(L(Dph))(-)/(L(Dph))(2-)/(L(Dph))(3-) for 5. Complex 6 is best formulated as a Sm(3+) compound with one "normal" (L(Tol,Ad))(-) and one deprotonated (L(Tol,Ad)-H)(2-) ligand.
新的 [Al(L(Tol))Br(2)] (1) 和已知的 [Al(L(Ph))Me(2)] (2) 被制备为更新型铝化合物的潜在前体。然而，只有后者是有效的。因此，2 和两个当量的钾是 [{Al(L(Ph))Me(2)K(2)(OEt(2))}(2)] (3) 的来源。配合物 [{KSm(L(Ph))(2)}(2)] (4)、[Sm(2)(L(Dph))(3)] (5) 和 [Sm(L(Tol,Ad))(L(Tol,Ad)-H)] (6) 是从 SmI(2) 和两个当量的合适的钾β-二酮腙 [L(Ph) 或 L(Tol) 或 L(Dph) = {N(SiMe(3))C(Ar)}(2)CH，Ar = Ph 或 C(6)H(4)Me-4 或 C(6)H(4)Ph-4；L(Tol,Ad) = N(SiMe(3))C(C(6)H(4)Me-4)C(H)C(Ad)NSiMe(3)，L(Tol,Ad)-H = N(SiMe(3))C(C(6)H(4)Me-4)C(H)C(Ad)NSiMe(2)CH(2)，Ad = 1- adamantyl] 得到的。晶体配合物 3-6 以非常低的（4，5）或满意的（3，6）产率分离出来，并通过 X 射线衍射进行了表征。通过比较 M-N、N-C、C-C 和 C-C(Ar)键长与合适的标准，配合物 3-5 被分配为含有 Al(3+)/(L(Ph))(3-) 的 3、Sm(3+)/(L(Ph))(-)/(L(Ph))(3-) 的 4 和 {Sm(3+)}(2)/(L(Dph))(-)/(L(Dph))(2-)/(L(Dph))(3-) 的 5。配合物 6 最好表示为具有一个“正常”(L(Tol,Ad))(-) 和一个去质子化的(L(Tol,Ad)-H)(2-)配体的 Sm(3+)化合物。
