Departamento de Química Orgánica e Inorgánica-IUQOEM, Universidad de Oviedo-CSIC, E-33071 Oviedo, Spain.
Dalton Trans. 2012 Jun 28;41(24):7249-57. doi: 10.1039/c2dt30583f. Epub 2012 May 9.
The reactions of [Ru(3)(CO)(12)] with four aromatic diazines have been studied in THF at reflux temperature. With phthalazine (L(1)), the compound [Ru(3)(μ-κ(2)N(2)N(3)-L(1))(μ-CO)(3)(CO)(7)] (1), which contains an intact phthalazine ligand in an axial position bridging an Ru-Ru edge through both N atoms, is initially formed but it reacts with more phthalazine to give [Ru(3)(κN(2)-L(1))(μ-κ(2)N(2)N(3)-L(1))(μ-CO)(3)(CO)(6)] (2), in which a π-π stacking interaction between the aromatic rings of both ligands determines their position in cluster axial sites on the same face of the Ru(3) triangle. With quinazoline (HL(2)), the cyclometalated hydrido decacarbonyl derivative [Ru(3)(μ-H)(μ-κ(2)N(3)C(4)-L(2))(CO)(10)] (3) is initially produced but it partially decarbonylates under the reaction conditions to give [Ru(6)(μ-H)(2)(μ-κ(2)N(3)C(4)-L(2))(μ(3)-κ(3)-N(1)N(3)C(4)-L(2))(CO)(19)] (4), which results from the displacement of a CO ligand of 3 by the uncoordinated N(1) atom of another molecule of 3. With 4,7-phenanthroline (H(2)L(3)), the stepwise formation of the cyclometalated derivatives [Ru(3)(μ-H)(μ-κ(2)N(4)C(3)-HL(3))(CO)(10)] (5) and two isomers of [Ru(6)(μ-H)(2)(μ(4)-κ(4)N(4)C(3)N(7)C(8)-L(3))(CO)(20)] (6a, 6b) takes place. In compounds 6a and 6b, two Ru(3)(μ-H)(CO)(10) trinuclear units are symmetrically (C(2) in 6a or C(S) in 6b) bridged by a doubly-cyclometalated 4,7-phenanthroline ligand. With 2,3'-bipyridine (HL(4)), two products have been isolated, [Ru(3)(μ-H)(μ-κ(2)N(3')C(4')-L(4))(CO)(10)] (7) and [Ru(3)(μ-H)(μ-κ(3)N(2)N(3')C(2')-L(4))(CO)(9)] (8). While compound 7 contains an N(3')C(4')-cyclometalated 2,3'-bipyridine, in compound 8 an N(3')C(2')-cyclometalation is accompanied by the coordination of the N(2) atom of the remaining pyridine fragment. The structures of compounds 2, 3, 4, 6a and 8 have been determined by X-ray diffraction crystallography.
[Ru(3)(CO)(12)]与四种芳族二嗪在 THF 回流温度下的反应已经过研究。与邻苯二甲嗪（L(1)）反应，最初形成了化合物[Ru(3)(μ-κ(2)N(2)N(3)-L(1))(μ-CO)(3)(CO)(7)]（1），其中一个完整的邻苯二甲嗪配体处于轴向位置，通过两个 N 原子桥接 Ru-Ru 边缘，但它会与更多的邻苯二甲嗪反应，生成[Ru(3)(κN(2)-L(1))(μ-κ(2)N(2)N(3)-L(1))(μ-CO)(3)(CO)(6)]（2），其中两个配体的芳环之间的π-π堆积相互作用决定了它们在 Ru(3)三角形同一面上的轴向位置。与喹唑啉（HL(2)）反应，最初生成了偕二氢的环金属化氢羰基衍生物[Ru(3)(μ-H)(μ-κ(2)N(3)C(4)-L(2))(CO)(10)]（3），但在反应条件下部分脱羰生成[Ru(6)(μ-H)(2)(μ-κ(2)N(3)C(4)-L(2))(μ(3)-κ(3)-N(1)N(3)C(4)-L(2))(CO)(19)]（4），这是由 3 的 CO 配体被另一个 3 分子的未配位的 N(1)原子取代的结果。与 4,7-菲咯啉（H(2)L(3)）反应，逐步形成了偕二氢的环金属化衍生物[Ru(3)(μ-H)(μ-κ(2)N(4)C(3)-HL(3))(CO)(10)]（5）和[Ru(6)(μ-H)(2)(μ(4)-κ(4)N(4)C(3)N(7)C(8)-L(3))(CO)(20)]（6a，6b）的两种异构体。在化合物 6a 和 6b 中，两个 Ru(3)(μ-H)(CO)(10)三核单元通过一个双环金属化的 4,7-菲咯啉配体以对称（6a 中的 C(2)或 6b 中的 C(S)）桥接。与 2,3'-联吡啶（HL(4)）反应，已分离出两种产物，[Ru(3)(μ-H)(μ-κ(2)N(3')C(4')-L(4))(CO)(10)]（7）和[Ru(3)(μ-H)(μ-κ(3)N(2)N(3')C(2')-L(4))(CO)(9)]（8）。虽然化合物 7 含有一个 N(3')C(4')-环金属化的 2,3'-联吡啶，但在化合物 8 中，N(3')C(2')-环金属化伴随着剩余吡啶片段的 N(2)原子的配位。化合物 2、3、4、6a 和 8 的结构已通过 X 射线衍射结晶学确定。
