Gold– and Platinum–Bismuth Donor–Acceptor Interactions Supported by an Ambiphilic PBiP Pincer Ligand

Abstract

Noble metals meet a heavyweight: A pincer ligand brings together bismuth with gold and platinum, so that metallophilic interactions are established. According to DFT calculations, these interactions contain dominant metal→bismuth contributions.

Novel zwitterionic complexes arising from the coordination of an ambiphilic phosphorus–aluminum ligand to gold

“…15 X-ray diffraction analysis (Fig. 3, left) confirmed that the two 40 phosphines are coordinated to gold in a quasi-linear arrangement (PAuP = 176.37(2)°). The chloride has been transferred from gold to aluminum.…”

“…7 The unique properties of aluminum, in particular its more 35 pronounced Lewis acid character compared to boron, makes phosphorus-aluminum ambiphilic ligands very appealing, but the relatively high sensitivity of the hitherto studied PAl (due to protonolysis or redistribution of Al-C bonds) 7a,9 represents a synthetic limitation. Thus, we became interested in exploring the 40 coordination chemistry of the geminal PAl compound Mes 2 PC(=CHPh)AltBu 2 1 that has shown good stability and unique behaviour towards a range of small molecules. 10, 11 Here, we report the synthesis and characterization of five new PAl complexes.…”

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).…”

Reprint of “Coordination chemistry of homoatomic ligands of bismuth, selenium and tellurium”

“…Considered from this perspective, the formula has to be organised as (Bi 10 )(AuEBi 3 X 9 ) 2 . Such gold-bismuth donor-acceptor interactions have recently been studied in a dinuclear complex with pincer ligands as well [71]. Numerous further examples of organometallic complexes with direct M Bi bonds are known.…”