Gold, [[1,1′-Biphenyl]-2-ylbis(1,1-dimethylethyl)phosphine]chloro- and Gold(1+), (Acetonitrile)[[1,1′-biphenyl]-2-ylbis(1,1-dimethylethyl)phosphine] (OC-6-11)-hexafluoroantimonate(1−)

Abstract

[854045-93-5] C20H27AuClP (MW 530.82) InChI = 1S/C20H27P.Au.ClH/c1-19(2,3)21(20(4,5)6)18-15-11-10-14-17(18)16-12-8-7-9-13-16;;/h7-15H,1-6H3;;1H/q;+1;/p-1 InChIKey = MZMOUYZCJIFYAH-UHFFFAOYSA-M (complex 1 mixed with Ag(I) salts leads to a very active catalyst for the cyclization of 1,n-enynes and activation of alkynes) Alternate Names: JohnPhos gold chloride complex;(2-biphenyl)di-tert-butylphosphine gold(I) chloride; 2-(di-tert-butylphosphino)biphenyl gold(I) chloride. Physical Data: mp 237–240 °C. Solubility: soluble in most organic solvents. Form Supplied in: white solid, widely available. Preparative Method: this complex is prepared following the general procedure for the synthesis of [AuCl(PR3)] complexes:2 sodium tetrachloroaurate(III) dihydrate (1.0 mmol) is dissolved in water and the orange solution is cooled to 0 °C in an ice bath. To this solution, 2,2′-thiodiethanol (3.0 mmol) is slowly added over 45 min with stirring. A solution of di-tert-butylbiphenylphosphine ligand (1.0 mmol) in EtOH is added dropwise to give a white solid. The solid is filtered , washed with MeOH, and dried in vacuo. Gold complex 1 is obtained in 43% yield.3 Handling, Storage, and Precautions: this complex is only moderately air sensitive and should be stored in a dry place. It has to be mixed with stoichiometric Ag(I) salts to form the active catalyst. Excess of silver salts can lead to undesired side reactions.1 [866641-66-9] C22H30AuF6NPSb (MW 772.17) InChI = 1S/C20H27P.C2H3N.Au.6FH.Sb/c1-19(2,3)21(20(4,5)6)18-15-11-10-14-17(18)16-12-8-7-9-13-16;1-2-3;;;;;;;;/h7-15H,1-6H3;1H3;;6*1H;/q;;+1;;;;;;;+5/p-6 InChIKey = ADQOZROJMVWPRI-UHFFFAOYSA-H (complex 2 contains a weakly coordinating acetonitrile ligand and is a very active catalyst in a variety of transformations; this complex allows performing catalytic reactions in the absence of Ag(I) salts) Alternate Names: (acetonitrile)[(biphenyl-2-yl)di-tert-butylphosphine]gold(1+) hexafluoroantimonate. Physical Data: mp 198–203 °C. Solubility: soluble in most organic solvents. Preparative Method: a mixture of neutral gold complex 1 (0.5 mmol) and AgSbF6 (0.5 mmol) is suspended in MeCN (4 mL). The mixture is stirred at 23 °C for 12 h, the solvent is evaporated, and the crude product is dissolved in MeCN (1 mL). The mixture is then filtered through a pad of Celite, and the solvent is evaporated under reduced pressure to give cationic complex 2 in 73% yield.1 Form Supplied in: white solid, widely available. Handling, Storage, and Precautions: this complex has been prepared as stable crystalline solid that can be handled under ordinary conditions. It should be stored in a dry place under N2.