Gold­(I) fluorido complexes with phosphine ligands have been synthesized from their respective iodido precursors. The bonding situation in comparison between complexes bearing phosphines and N-heterocyclic carbenes (NHCs) was explored quantum-chemically, obtaining similar results for both. Calculations of the 19F NMR chemical shifts match the experimental values well, including the approximately 40 ppm low-field shifts for the phosphine complexes compared to the NHC complexes, in spite of similar negative charges on fluorine. The reactivity of the highly water-sensitive gold­(I) fluorido complexes was studied, resulting in substitution at the metal using trimethylsilyl reagents. The compounds studied were characterized using NMR as well as X-ray diffraction methods.

This communication describes an efficient palladium pincer complex-catalyzed allylic C-H borylation of alkenes. The transformation exhibits high regio- and stereoselectivity with a variety of linear alkenes. A synthetically useful feature of this allylic C-H borylation method is that all allyl-Bpin products can be isolated in usually high yields. Preliminary mechanistic studies indicate that this C-H borylation reaction proceeds via Pd(IV) pincer complex intermediates.

The germylium ions [GeR3]+ catalyze dehydrodefluorination reactions of fluorinated alkanes when germanes are used as hydrogen source.

The hydrogen bonding in the Au(I) complex [Au(F • HF)(SPhos)] (SPhos = dicyclohexyl(2',6'-dimethoxy[1,1'-biphenyl]-2yl)phosphane) (1 a • HF) has been analysed by IR and NMR measurements, revealing the formation of an unsymmetrical bifluoride moiety. The data are in excellent agreement with DFT calculations. Comparisons to analogous complexes bearing NHC (NHC = N-heterocyclic carbene) ligands demonstrated a comparable bonding situation. The identity of the halogen bond in the compound [Au(F • IC 6 F 5 )(SPhos)] (1 a • IC 6 F 5 ) in CD 2 Cl 2 has been estimated, and van't Hoff data for the equilibrium between [Au(F)(SPhos)] (1 a) and IC 6 F 5 with [Au(F • IC 6 F 5 )(SPhos)] are ΔH 0 = À 8.1(3) kJ mol À 1 and ΔS 0 = À 36(1) J (mol K) À 1 . The latter are also in agreement with DFT calculations. For all calculations, comparisons between an explicit and implicit solvent model were drawn. Single crystal X-ray diffraction studies were performed for [Au(F • 2IC 6 F 5 )(BrettPhos)] • 2IC 6 F 5 (BrettPhos = 2-(dicyclohexylphosphino)-3,6-dimethoxy-2',4',6'triisopropyl-1,1'-biphenyl) (1 b • 4IC 6 F 5 ) demonstrating the presence of halogen bonds to Au(I) fluorido complexes in the solid state.

The Au I complex [Au{N(F)SO 2 Ph}(SPhos)] (SPhos = dicyclohexyl(2',6'-dimethoxy[1,1'-biphenyl]-2yl)phosphane) (2) bearing a fluoroamido ligand has been synthesized by reaction of the fluorido complex [Au(F)(SPhos)] (1) with NFSI (NFSI = N-fluorobenzenesulfonimide). A reaction with CO resulted in an unprecedented insertion into the NÀ F bond at 2. With the carbene precursor N 2 CH(CO 2 Et) NÀ F bond cleavage gave the AuÀ F bond insertion product [Au{CHF-(CO 2 C 2 H 5 )}(SPhos)] (7). The presence of CNtBu led to AuÀ N cleavage at 2 and concomitant amide formation to give the cationic complex [Au(CNtBu)(SPhos)][N-(F)SO 2 Ph)] ( 5), which reacted further to give FtBu as well as the cyanido complex [Au(CN)(SPhos)] ( 6). These results led to the development of a process for the amination of electrophilic organic substrates by transfer of the fluoroamido group NF(SO 2 Ph) À .