A tridentate ligand, pyphos (6-diphenylphosphino-2-pyridonato), was utilized to prepare tetrametal complexes since this ligand has unique coordinating sites comprised of three different elements, i.e., phosphorus, nitrogen, and oxygen, in almost linear fashion. By using pyphos ligand, linearly aligned tetrametal complexes of group 10 metals [Mo2M2(pyphos)4X2n] (M = Pt and Pd; n = 0, 1, and 2) were prepared, and for group 9 metals, [Mo2M2(pyphos)4(RNC)4X2n]2+ (M = Ir and Rh; n = 0 and 1). Fully metal-to-metal bonded complexes were obtained by reduction of MII to MI for group 10 metals and by oxidation of MI to MII for group 9 metals. Both reactions afforded complexes having unique M–Mo≡Mo–M skeletons, i.e., metalla-2-butyne. Structural and chemical properties were systematically investigated for M0 (M = Pt and Pd) and MI (M = Ir and Rh). Thus, oxidative reactions of Pd0 complexes [Mo2Pd2(pyphos)4] and IrI complexes [Mo2Ir2(pyphos)4(RNC)4]2+ with RX or X2 were studied and unique 1,4-addition reaction was demonstrated. Dichromium complexes analogous to dimolybdenum complexes were prepared and axial donation of PtMe2 moiety significantly elongated the Cr–Cr bond, due to the dative bonding interaction between CrII and PtII units.
我们利用三叉
配体 pyphos(6-
二苯基膦-2-
吡啶)来制备四
金属配合物,因为这种
配体具有独特的配位位点,由
磷、氮和氧三种不同元素组成,几乎呈线性排列。通过使用
吡磷配体,制备出了第 10 族
金属的线性排列四
金属配合物 [Mo2M2(pyphos)4X2n](M = Pt 和 Pd;n = 0、1 和 2),以及第 9 族
金属的 [Mo2M2(pyphos)4(RNC)4X2n]2+(M = Ir 和 Rh;n = 0 和 1)。对于第 10 族
金属,通过将 MII 还原成 MI,而对于第 9 族
金属,则通过将 MI 氧化成 MII,得到了完全
金属对
金属结合的络合物。这两种反应都得到了具有独特 M-Mo≡Mo-M 骨架的络合物,即
金属-
2-丁炔。对 M0(M = Pt 和 Pd)和 MI(M = Ir 和 Rh)的结构和
化学特性进行了系统研究。因此,研究了 Pd0 复合物[Mo2Pd2(pyphos)4]和 IrI 复合物[Mo2Ir2(pyphos)4(RNC)4]2+ 与 RX 或 X2 的氧化反应,并证明了独特的 1,4 加成反应。研究人员制备了类似于二
钼络合物的重
铬络合物,由于 CrII 和 PtII 单元之间的成键作用,PtMe2 分子的轴向捐赠显著延长了 Cr-Cr 键。