Laboratorium für Organische Chemie, Eidgenössische Technische Hochschule (ETH) Zürich, CH-8093 Zürich, Switzerland.
J Am Chem Soc. 2009 Apr 22;131(15):5675-90. doi: 10.1021/ja900449y.
The organoplatinum(II) complexes [(NN)PtMe(2)] and [(NN)PtPh(2)] (NN = ArNC(Me)C(Me)NAr, Ar = 2,6-dichlorophenyl) can act as donor ligands for copper(I) and silver(I) triflates, affording a series of homo- and heteroleptic complexes which were characterized by X-ray diffraction. [(NN)PtMe(2)] binds to the coinage metals through short, ligand-unsupported d-d(10) contacts that are best described as Pt-->M dative bonds (M = Cu, Ag), in which the d(z(2)) orbital of the square-planar Pt(II) center donates electron density to the Lewis-acidic metal. Spectroscopic studies in solution and DFT calculations corroborate this description. [(NN)PtPh(2)] binds preferentially by eta(1) or eta(2) complexation of the ipso carbon atoms of the phenyl groups to the coinage metal, affording homoleptic complexes {(NN)PtPh(2)M}(+){TfO}(-) in the solid state. The 1:1 adducts of formula {[(NN)PtPh(2)]M(OTf)}(n) (M = Cu, n = 1; M = Ag, n = 2) are observed in solution, and a 1:2 adduct of formula {[(NN)PtPh(2)]Ag(2)(OTf)(2)(C(6)H(6))}(n) was characterized in the solid state, showing that unsupported Pt-->M bonds are also accessible for [(NN)PtPh(2)]. The thermolyses of the complexes [(NN)PtMe(2)]MOTf in benzene affords moderate yields of [(NN)PtPh(2)] through an oxidatively induced double C-H activation process.
有机铂(II)配合物[(NN)PtMe2]和[(NN)PtPh2]（NN=ArNC(Me)C(Me)NAr，Ar=2,6-二氯苯基）可以作为铜(I)和银(I)三氟甲磺酸的给体配体，形成一系列同系物和杂系物配合物，这些配合物通过 X 射线衍射进行了表征。[(NN)PtMe2]通过短的、无配体支持的 d-d(10)接触与贵金属结合，这种接触最好被描述为 Pt-->M 配位键（M=Cu，Ag），其中平面正方形 Pt(II)中心的 d(z(2))轨道向路易斯酸性金属提供电子密度。溶液中的光谱研究和 DFT 计算证实了这一描述。[(NN)PtPh2]通过苯环的 ipso 碳原子优先通过 eta(1)或 eta(2)配位与贵金属结合，在固态中提供同系物配合物{(NN)PtPh2M}{TfO}(-)。观察到化学式为{[(NN)PtPh2]M(OTf)}(n)（M=Cu，n=1；M=Ag，n=2）的 1:1 加合物在溶液中存在，化学式为{[(NN)PtPh2)]Ag(2)(OTf)(2)(C(6)H(6))}(n)的 1:2 加合物在固态中被表征，表明[(NN)PtPh2)]也可以形成无支持的 Pt-->M 键。在苯中，配合物[(NN)PtMe2)]MOTf 的热解通过氧化诱导的双重 C-H 活化过程以中等产率得到[(NN)PtPh2)]。
