Metallophilic Contacts in 2-C₆F₄PPh₂Bridged Heterobinuclear Complexes: A Crystallographic and Computational Study

Abstract

Treatment of the bis(chelate) complex trans-[Pd(κ(2)-2-C6F4PPh2)2] (7) with PMe3 gave trans-[Pd(κC-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(μ-2-C6F4PPh2)2MCl] [M = Cu (14), Ag (15), Au (16)], from which the corresponding salts [(Me3P)2Pd(μ-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(μ-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(μ-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) Å] suggestive of attractive noncovalent (dispersion) interactions, a conclusion that is supported by theoretical calculations of the electron localization function and the noncovalent interactions descriptor.

A Phosphine Functionalized β‐Diketimine Ligand for the Synthesis of Manifold Metal Complexes

“…The gold phosphorous distances in 4 (Au−P1 2.3069(13), Au−P2 2.3212(14) Å) are shorter in comparison to the silver phosphorous bond distances in 3 (Ag−P1 2.3818(9), Ag−P2 2.3994(9) Å), yet slightly longer than those in 2 (Au1−P1 2.2724(7), Au2−P2 2.2793(7) Å). The obtained data of both structures is in line with comparable bis‐triarylphosphine complexes of Ag I and Au I …”

“…The obtained data of both structuresi sinline with comparable bis-triarylphosphine complexes of Ag I and Au I . [57][58][59] Furthermore,t he isostructural compounds 3 and 4 werei nvestigated by NMR andI Rs pectroscopy. In the 31 P{ 1 H} NMR spectrum( CDCl 3 )o fAu I compound 4 asingle resonance, significantly downfield shifted compared to ligand 1 (d = À14.5 ppm), is detected at d = 34.5 ppm, indicating asole symmetric phosphine gold interaction.…”

Experimental and DFT Study of the [AuAr(AsPh3)]-Catalyzed cis/trans Isomerization of [PdAr2(AsPh3)2] (Ar = C6F5 or C6Cl2F3): Alternative Mechanisms and Its Switch upon Pt for Pd Substitution

“…Since that seminal study, a number of complexes have been reported for systems with M = Pd II , Pt II and M' = Au I , Ag I , Cu I , [4][5][6][7][8][9][10][11][12] containing Pd-Au interactions that resemble, more or less closely, the M-M' interactions proposed in reference 1 for the intermediates or transition states shown in Scheme 1. It might look far-fetched to think that the exchange (and isomerization) model based on formation of M-M' interactions at short distances could be found for less similar metal centers, but the fact is that in our theoretical mechanistic studies on the ZnMe2-catalyzed cis/trans isomerization of [PdMeAr(PR3)2] complexes (Ar = C6Cl2F3 and C6F5) we found Zn II playing a structural role quite similar to that of Au I in Scheme 1.…”

Metallophilic Mercuraazamacrocycles Derived from Bis{6‐formyl‐(2,3,4‐trimethoxy)phenyl}mercury: Reactivity with d10and d8Metal Ions

“…The complexes showing aurophilic (Au ··· Au) interactions have been widely studied . Other than Au I , metal ions such as Ag I , Hg II , Cu I , Pd II , Pt II , Ga I , In I , Tl I are also known to involve in homo‐/hetrometallic metallophilic interactions …”