From Diphosphane to Diphosphodiide Gold(III) Derivatives of 1,2‐Diphosphinobenzene

Abstract

Treatment of 1,2-diphosphinobenzene with [Au(C6F5)3(tht)] leads to the diphosphane derivative [{Au(C6F5)3}(1,2-PH2C6H4PH2)] (1), which further reacts with other pentafluorophenylgold(III) reagents in the presence of acetylacetonate as deprotonating agent to afford phosphane-phosphide complexes. The noncyclic PPN[{Au(C6F5)3}2(1,2-PHC6H4PH2)] (2; PPN = bis(triphenylphosphine)iminium) has been shown to be a useful starting material for the synthesis of higher nuclearity cyclic or noncyclic diphosphide or even diphosphodiide derivatives through similar reactions. The crystal structures of the trinuclear anionic NBu4[{Au(C6F5)3}(1,2-PHC6H4PH){Au(C6F5)2Cl}{mu-Au(C6F5)2}] (3) and the hexanuclear [{Au(C6F5)3}(1,2-PC6H4P){Au(C6F5)3}{mu-M(dppe)M}2] (M = Au (12), Ag (13)) have been established by X-ray diffraction methods, the last complexes having a bicyclic ring containing three intramolecular interactions between the M(I) centres.

Perfluoroarylgold complexes

“…The usual method for displacing the labile ligand tht by phosphorus donor ligands extensively employed with a variety of tertiary phosphines has also been used recently for the synthesis of pentafluorophenyl complexes containing primary or secondary phosphines, such as diphenylphosphine [97,98], phenylphosphine [99] or 1,2-diphosphinobenzene [100]. Thus, the gold(I) or gold(III) phosphino derivatives [Au(C 6 F 5 )(LH)] (LH = PPh 2 H, PPhH 2 ), [Au(C 6 F 5 ) 3 (LH)] (LH = PPh 2 H, PPhH 2 , 1,2-C 6 H 4 (PH 2 ) 2 ) or trans-[Au(C 6 F 5 ) 2 (PPh 2 H) 2 ]ClO 4 have been described, the latter showing a trans disposition of the ligands as its IR spectrum indicates [97] (see Scheme 12).…”

“…A number of cyclic or non-cyclic gold(III) phosphinophosphides or diphosphides were synthesized from 1,2-diphosphinobenzene (Scheme 16) [100]. The diphos-…”

Gold–Gold Interactions

“…Each dppe bridges two gold(I) centers which are connected through aurophilic interactions. Another gold-gold interaction joins two gold(I) atoms, each of them bonded to a different dppe [187] . …”

Gold Phosphide Complexes

“…46 The diphosphino complex [{Au(C 6 F 5 ) 3 }(1,2-PH 2 C 6 H 4 PH 2 )] or the phosphane-phosphide [{Au(C 6 F 5 ) 3 } 2 (1,2-PHC 6 H 4 PH 2 )]…”

“…[{Au(C 6 F 5 ) 3 } 2 (1,2-PHC 6 H 4 PH 2 )] -has also been shown to be a useful starting material for the synthesis of mixed Au III /M I (M = coinage metal) diphosphide or diphosphodiide compounds following a similar synthetic strategy. 46 Thus, its reaction with phosphino-or pentafluorophenylgold(I) or silver(I) complexes in the presence of the same deprotonant agent leads to trinuclear diphosphides displaying a tricoordinated gold(I) or silver(I) centre (see scheme 7). The bridging chlorine atom of [{Au(PPh 3 )} 2 (µ-Cl)]…”