The Effect of Substituents at Lewis Acidic Bismuth(III) Centers on Its Propensity to Bind a Noble Metal Donor

Abstract

To investigate the effect of X in ambiphilic compounds BiX(o-PPh2-C6H4)2, PBiP-X, on metallophilic Pt-Bi interactions in its PtCl2 complexes two new derivatives PBiP-Me and PBiP-C6F5 were synthesized. Reaction with dichloro(1,5-cyclooctadiene)platinum(II) led to the platinum(II) complexes [PtCl2(PBiP-Me)], 3, and [PtCl2(PBiP-C6F5)], 4, which together with the halide [PtCl2(PBiP-Cl)], 2, reported previously, establish a series of related PBiP-X complexes differing only in X. This could be complemented by accessing [PtCl2(PBiP-OTf)], 5, through the reaction of 2 with AgOTf. Analysis of the geometrical and electronic structures of these complexes revealed that in all cases the platinum(II) centers act as donors (through their filled d(z(2)) orbitals) to the bismuth(III) centers (possessing σ*(Bi-X)/6p acceptor orbitals). The strength of these interactions increases with increasing electron-withdrawing character of X, which supports the conceptual approach in constructing this new class of compounds.

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

“…The Lewis acidity of Bi III in an ambiphilic PBiP ligand system (Ph 2 P‐C 6 H 4 ‐Bi(Cl)‐C 6 H 4 ‐PPh 2 ), employed as such or generated in situ, was exploited to bind Au I , Pt II and Pd II centers, which acted as σ donors. It was further shown that upon replacement of the Cl residue at Bi against less electronegative ligands, the character of the bismuthane changed from acceptor to predominantly donor …”

“…character of the bismuthane changed from acceptor to predominantly donor. [7] The insights gained tethering bismuthane functions with phosphane units as in the PBiP ligand mentioned above for the complexation of late transition metals, led us to pursue further promisingb ismuthane/phosphane combinations. The xantheneb ackbone has been used for the construction of av ariety of potent bidentate ligands and complexes that exhibit interesting reactivity.…”

How Changing the Bridgehead Can Affect the Properties of Tripodal Ligands

“…At the top of the group (N and P) the higher electronegativity,c ombined with the presence of compact lone pairs,i sk nown to lead to ambidentate character in which both the N-atoms of the 2-py groups and the Group 15 atom (E) can donate to metal ions ( Figure 2b). [32][33][34][35][36] The increase in the Lewis acidity of the bridgehead atoms in 1-3 was demonstrated by initial DFT (B3LYP/def2-TZVPP) calculations of their fluoride ion affinities (see the Supporting Information). [32][33][34][35][36] The increase in the Lewis acidity of the bridgehead atoms in 1-3 was demonstrated by initial DFT (B3LYP/def2-TZVPP) calculations of their fluoride ion affinities (see the Supporting Information).…”

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.…”