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Heteronuclear Rhodium,Palladium,Platinum,and Gold Organoimido Complexes from Dinuclear Organoamido Rhodium Precursors

机译:双核有机氨基铑前体的异核铑,钯,铂和金有机亚氨基配合物

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Treatment of the organo-amido complexes[Rh_2(|Li-4-cies[Li_2Rh_2(|Li-4-NC_6H_4Me)_2(L_2)_2].Further reaction of[Li_2Rh_2(Li_2-4-NC_6H_4Me)_2(cod)_2]with[Rh_2(mu-Cl)_2(cod)_2]afforded the neutral tetra-nuclear complex[Rh_4(mu4-NC_6H_4Me)_2-(cod)_4](2),which rationalizes the direct syntheses of 2 from[Rh_2(mu-Cl)_2(cod)_2]and Li_2NC_6H_4Me.Reactions of[Li_2Rh_2(mu-4-NC_6H_4Me)_2(CO)_4]with chloro complexes such as[Rh_2(mu-C1)_2(CO)_4],[MCl_2(cod)](M-Pd,Pt),and[Ru_2(mu-Cl)_2Cl_2(p-cymene)_2]afford-ed the homo- and heterotrinuclear complexes PPN[Rh_3(mu,-4-NC_6H_4Me)_2-(CO)_6](5;PPN=bis(triphenylphos-phine)iminium),[(CO)_4Rh_2(mu-4-NC_6H_4Me)_2M(cod)](M-Pd(6),Pt(7))and[(CO)_4Rh_2(mu-4-NC_6H_4Me)_2Ru(p-cymene)](8),while the reaction with[AuCl(PPh_3)]gave the tetranuclear compound[(CO)_4Rh_2(mu-4-NC_6H_4Me)_2{Au(PPh_3)}_2](9).The structures of complexes 6,8,and 9 were determined by X-ray dif fraction studies.The anion of 5 reactswith[AuCl(PPh_3)] to give the butterfly cluster[{Rh_3(mu-4-NC_6H_4Me)_2(CO)_6}-Au(PPh_3)](10),in which the Au atomis bonded to two rhodium atoms.Reaction of the anion of 5 with[Rh(cod)(NCMe)_2](BF_4)gave the tetranuclear complex[Rh_4(mu,-4-NC_6H_4Me)_2(CO)_6(cod)](11)in whichthe Rh(cod) fragment is pi-bonded to one of the arene rings,while the reaction of the anion of 5 with[PdCl_2(cod)]afforded the heterotrinuclear complex 6 through a metal exchange process.
机译:有机-氨基配合物[Rh_2(| Li-4-cies [Li_2Rh_2(| Li-4-NC_6H_4Me)_2(L_2)_2])的处理。[Li_2Rh_2(Li_2-4-NC_6H_4Me)_2(cod)_2的进一步反应[Rh_2(mu-Cl)_2(cod)_2]与[Rh_4(mu4-NC_6H_4Me)_2-(cod)_4](2)相适应的中性四核配合物,使[Rh_2]的直接合成合理化(mu-Cl)_2(cod)_2]和Li_2NC_6H_4Me。[Li_2Rh_2(mu-4-NC_6H_4Me)_2(CO)_4]与氯络合物如[Rh_2(mu-C1)_2(CO)_4]的反应, [MCl_2(cod)](M-Pd,Pt)和[Ru_2(mu-Cl)_2Cl_2(p-cymene)_2]负载同型和异型三核复合物PPN [Rh_3(mu,-4-NC_6H_4Me) _2-(CO)_6](5; PPN =双(三苯基膦)亚胺),[[CO)_4Rh_2(mu-4-NC_6H_4Me)_2M(cod)](M-Pd(6),Pt(7) )和[(CO)_4Rh_2(mu-4-NC_6H_4Me)_2Ru(对甲基苯甲基)](8),而与[AuCl(PPh_3)]的反应得到四核化合物[(CO)_4Rh_2(mu-4-NC_6H_4Me )_2 {Au(PPh_3)} _ 2](9)。通过X射线衍射研究确定复合物6,8和9的结构。5的阴离子与[AuCl(PPh_3)]反应生成蝴蝶簇[{Rh_3(mu-4-NC_6 H_4Me)_2(CO)_6} -Au(PPh_3)](10),其中Au原子与两个铑原子键合。5阴离子与[Rh(cod)(NCMe)_2](BF_4)的反应四核配合物[Rh_4(mu,-4-NC_6H_4Me)_2(CO)_6(cod)](11),其中Rh(cod)片段被π键键合到一个芳烃环上,而阴离子的反应具有[PdCl 2(cod)]的5通过金属交换过程提供了异三核配合物6。

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