Miguel M. Alvarez-Falcon

New arenediethynylgold(I) complexes. Crystal structures of [Ph3PAuCC(phenylendiyl-1,3)CCAuPPh3] and [Ph3PAuCC(mesitylendiyl-1,3)CCAuPPh3]

By reacting the dialkynes HCC(Ar)CCH [Ar=1,3-C6H4 (mphen), 1,3-(C6HMe3-2,4,6) (mes), 1,4-(C6Me4-2,3,5,6) (dur)] with [AuClL] [L=dimethylsulfide (dms), tetrahydrothiophene (tht)] in the presence of an excess of Et3N the polymeric complexes [AuCC(Ar)CCAu]n [Ar=mphen (1), mes (2) dur (3)] were prepared. Upon reaction of these complexes with two equivalents of phosphine or isocyanide ligands (L), complexes [LAuCC(Ar)CCAuL] [Ar=mes, L=tBuNC (4), XyNC (5); Ar=dur, L=PPh3 (6), tBuNC (7)] were prepared in good yields. The complex [tBuNCAuCC(mphen)CCAuCNtBu] (8) was prepared by reaction of the corresponding diethynylarene with 2 equiv. of [AuCl(CNtBu)] in the presence of NEt3. By reacting the appropriate diethynylarene with 2 equiv. of [Au(acac)PPh3], complexes [Ph3PAuCC(Ar)CCAuPPh3] [Ar=mphen (9), mes (10)] were prepared. The carbene complex [(tBuNH)(Et2N)CAuCC(mes)CCAuC(NHtBu)(NEt2)] (11) was obtained by reacting the corresponding isocyanide complex 4 with diethylamine. The crystal structures of complexes 9 and 10 have been determined by X-ray diffraction studies. In both cases one of the gold atoms is in an essentially linear environment [CAuP: 176.95(14) (9), 177.19(8)° (10)] while the other CAuP bond angle is appreciably bent [170.07(11) (9), 171.22(8)° (10)].

Synthesis and X-ray crystal structure of an anionic heteronuclear metallamacrocyclic triangle

trans-[Pt(C[triple bond]C(Ar)C[triple bond]CH)2(PMe3)2](Ar = C(6)Me(4)-3,4,5,6) (1) reacts with PPN[Au(acac)(2)](Hacac = acetylacetone; 1 : 1.16 molar ratio; PPN = (Ph3P)2N) to give PPN[(Au[Pt(PMe3)2]2)(mu-Ar(C[triple bond]C)2)3] (2) the crystal structure of which showed the anions as quasi equilateral triangles stacked parallel to each other through C-HAu interactions, resulting in channels of rhombic cross-section.

The first anionic arenediethynylgold(I) complexes

Abstract We report synthetic methods for the preparation of mono-, di-, tri- and polyanionic alkynylgold(I) complexes, derived from diethynylarenes. The reaction between PPN[Au(acac) 2 ] and 1,3-diethynylbenzene [HCC(mphen)CCH] (1:1 M ratio) afforded the polymeric complex (PPN) n [Au{CC(mphen)CC}] n ( 1 ) while the monomeric complexes (PPN)[Au{CC(Ar)CCH} 2 ] [Ar=mphen ( 2 ), mes ( 3 )] resulted when the same dialkyne or 1,3-diethynylmesitylene [HCC(mes)CCH] were used in a 1:2 M ratio. Complexes PPN[XAuCC(Ar)CCH] [Ar=mphen, X=Cl ( 4 ), Ar=mes, X=Cl ( 5 ), SCN ( 6 )] were obtained from the metathesis reactions between complexes 2 or 3 and the appropriate PPN[AuX 2 ] salts. The CCH groups in complexes 2 or 4 are acidic enough as to react with [Au(acac)PPh 3 ] (1:2) or with PPN[Au(acac) 2 ] (1:1) to give complexes PPN[Au{CC(mphen)CCAuPPh 3 } 2 ] ( 7 ) or (PPN) 3 [Au{CC(mphen)CCAuCl} 2 ] ( 8 ), respectively. Complexes (PPN) 2 [XAuCC(Ar)CCAuX)] [Ar=mphen, X=Cl ( 9 ); Ar=mes, X=Cl ( 10 ), SCN ( 11 )] have been prepared by reacting [Ph 3 PAuCC(mphen)CCAuPPh 3 ] with PPN[AuCl 2 ] (1:2) ( 9 ) or [AuCC(mes)CCAu] n with the appropriate PPNX (1:2) salt ( 10 , 11 ).