Data from: Metallophilic Contacts in 2‑C6F4PPh2 Bridged Heterobinuclear Complexes: A Crystallographic and Computational Study

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Treatment of the bis(chelate) complex trans-[Pd(kappa(2)-2-C6F4PPh2)2] (7) with PMe3 gave trans-[Pd(kappaC-2-C6F4PPh2)2(PMe3)2] (13) as a mixture of syn- and anti-isomers. Reaction of 13 with CuCl, AgCl, or [AuCl(tht)] (tht = tetrahydrothiophene) gave the heterobinuclear complexes [(Me3P)2Pd(mu-2-C6F4PPh2)2MCl] [M = Cu (14), Ag (15), Au (16)], from which the corresponding salts [(Me3P)2Pd(mu-2-C6F4PPh2)2M]PF6 [M = Cu (17), Ag (18), Au (19)] could be prepared by abstraction of the chloro ligand with TlPF6; 18, as well as its triflato (20) and trifluoroacetato (21) analogues, were also prepared directly from 13 and the appropriate silver salt. Reaction of 13 with [AuCl(PMe3)] gave the zwitterionic complex [(Me3P)PdCl(mu-2-C6F4PPh2)2Au] (24) in which the 2-C6F4PPh2 ligands are in a head-to-head arrangement. In contrast, the analogous reaction with [AuCl(PPh3)] gave [(Ph3P)PdCl(mu-2-C6F4PPh2)2Au] (25) with a head-to-tail ligand arrangement. Single crystal X-ray diffraction studies of complexes 14-21 show short metal-metal separations [2.7707(11)-2.9423(3) A] suggestive of attractive noncovalent (dispersion) interactions, a conclusion that is supported by theoretical calculations of the electron localization function and the noncovalent interactions descriptor.

本附件文件为关联学术文章提供补充数据。将双螯合配合物反式-[Pd(κ²(kappa(2))-2-C₆F₄PPh₂)₂]（7）与三甲基膦（PMe₃）反应，得到反式-[Pd(κC-2-C₆F₄PPh₂)₂(PMe₃)₂]（13），该产物为顺式（syn-）与反式（anti-）异构体的混合物。配合物13分别与氯化亚铜（CuCl）、氯化银（AgCl）或[AuCl(tht)]（其中tht代表四氢噻吩（tetrahydrothiophene））反应，得到异双核配合物[(Me₃P)₂Pd(μ-2-C₆F₄PPh₂)₂MCl] [M = Cu（14）、Ag（15）、Au（16）]；以六氟磷酸亚铊（TlPF₆）脱去该类配合物中的氯配体，即可制备得到相应的六氟磷酸盐[(Me₃P)₂Pd(μ-2-C₆F₄PPh₂)₂M]PF₆ [M = Cu（17）、Ag（18）、Au（19）]。其中配合物18及其三氟甲磺酸根配位（triflato，20）、三氟乙酸根配位（trifluoroacetato，21）的类似物，也可直接由13与对应银盐反应制得。配合物13与[AuCl(PMe₃)]反应得到两性离子配合物[(Me₃P)PdCl(μ-2-C₆F₄PPh₂)₂Au]（24），该配合物中2-C₆F₄PPh₂配体采取头对头（head-to-head）排列模式。与之相反，配合物13与[AuCl(PPh₃)]（三苯基膦（PPh₃））的类似反应则得到配体采取头对尾（head-to-tail）排列的[(Ph₃P)PdCl(μ-2-C₆F₄PPh₂)₂Au]（25）。对配合物14~21开展单晶X射线衍射（single crystal X-ray diffraction）分析，结果显示其存在较短的金属-金属间距[2.7707(11)~2.9423(3) Å]，提示体系中存在吸引力型非共价（色散）相互作用；这一结论通过电子定域函数（electron localization function）与非共价相互作用描述符（noncovalent interactions descriptor）的理论计算得到了验证。