PBiP Pincer Complexes of Platinum, Palladium, and Iridium Featuring Metal–Metal Bonds Synthesized by Oxidative Addition of Bismuth–Halide Bonds

Abstract

The compound BiCl(o-PPh 2 -C 6 H 4 ) 2 , PBiP-Cl, which in previous work had been shown to form complexes with pronounced M→Bi character, when metal(I) ions of group 11 or Pt II and Pd II ions were coordinated, behave differently in contact with late metal atoms in low oxidation states, known to easily undergo oxidative additions: Treatment of PBiP-Cl with M(PPh 3 ) 4 , with M = Pt, Pd, led to the formal insertion of M into the Bi−Cl bond to yield complexes [MCl(PBiP)]. Analogues PBiP-X with X = Br, I that could be accessed behaved similarly, producing [MX(PBiP)]. Both types of complexation reactionscoordination of PBiP-Cl as an ambiphilic ligand and oxidative additionwere observed to occur when [Ir(acac)(cod)] was chosen as the precursor compound. NMR investigations clearly indicated the presence of [Ir I (acac)(PBiP-Cl)] and [Ir III (acac)Cl(PBiP)] beside each other in solution, from which, however, only [Ir III (acac)Cl(PBiP)] could be crystallized. DFT results showed that both products differ only slightly in energy. Reaction of PBiP-Cl with [Ir(acac-F 6 )(cod)] led only to the iridium(III) product, underlining that electronic effects sensitively influence the course of reactivity and the position of the equilibrium.

Platinum Complexes Bearing a Tripodal Germyl Ligand

“…[5m], [6h], For main‐group III and V elements as the anchor atom, it has been found that heavier atoms can act as stronger electron acceptors than their lighter homologues and that the binding type depends on the metal center itself and its oxidation state. [6n], [7b], Similar results were obtained for tripodal ligands bearing heavier main‐group IV elements as the anchor atom (Ge, Sn) bonded to group 11 metals. [7b] Nevertheless, there are indications that light main‐group III or V elements mainly act as Lewis acids[6e], [6l], or Lewis bases, respectively, whereas light main‐group IV elements (C and Si) bond to the metal center with predominantly covalent bond character.…”

Bismuthanes as Hemilabile Donors in an O2‐Activating Palladium(0) Complex

“…Bearing in mind the scarcity of complexes with Pd ⋅⋅⋅ Bi interactions (apart from a cluster and a complex containing Pd−Bi metal bonds, only a Pd II →Bi complex of the above‐mentioned ambiphilic pincer ligand is known) the potential of Xan(PPh 2 )(BiPh 2 ) to bind Pd 0 was investigated. Therefore, a mixture of Xan(PPh 2 )(BiPh 2 ) and 0.25 equivalents of [Pd 2 (dba) 3 ] (dba=bis(dibenzylideneacetone)) was dissolved in tetrahydrofuran, and a color change from dark red to yellow was observed within a few minutes (Scheme ).…”

LCu(μ-X)2CuL compounds: An induced cuprophilic interaction

“…NBO analysis has been shown by many groups to be highly useful when analyzing weak to moderate bonding interactions such as ligand-metal donor-acceptor interactions 53,54 and metallophilic interactions. 10,41,[55][56][57] The monomers corresponding to 1(Me) (1-mon), 1-H(Me) Table 4, the Wiberg Bond Indices are in Table 5, and second-order perturbation energies in Table 6. Inspection of these three tables shows that each of the theoretical methods reproduces the same trends, and the methods behave as expected.…”