María-Teresa Chicote

2-[(Dimethylamino)methyl]phenylgold(III) complexes

[Hg(2-C6H4CH2NMe2)Cl] reacts with Me4N[AuCl4] or with [AuCl3(tht)] (tht = tetrahydrothiophene) in the presence of Me4NCl to give [Au(2-C6H4CH2NMe2)Cl2]. The same complex can also be obtained by treating [Hg(2-C6H4CH2NMe2)2] with Me4N[AuCl4]. The reactions of [Au(2-C6H4CH2NMe2)Cl2] with (i) KBr, KI or AgOOCCH3 give [Au(2-C6H4CH2NMe2)X2] (X = Br, I, OOCCH3), (ii) with PPh3 give [Au(2-C6H4CH2NMe2)Cl(PPh3)]Cl and (iii) with AsPh3, py or tht in the presence of NaClO4 lead to the cationic complexes [Au(2-C6H4CH2NMe2)Cl(L)]ClO4.

Synthesis of silver(I) complexes with carbonyl-stabilized phosphorus ylides: crystal structures of two [Ag{;CH(PPh3)C(O)R};2]+ derivatives

Reactions between AgX (X  ClO4, NO3) and ylides of the type Ph3PCHC(O)R (R &.dbnd; Me, Ph, OMe, OPh) in the molar ratio sol12 lead to complexes [Ag{;CH(PPh3)C(O)R};2]X; X-ray structure determinations have been carried out on two such complexes (R &.dbnd; OEt, X &.dbnd; ClO4 and R &.dbnd; OPh, X &.dbnd; NO3). Two of the silver ylide complexes react with [Au(acac)(PPh3)] (acac &.dbnd; acetylacetonate) in the molar ratio sol12 to give complexes [Ag{;C(PPh3)(CO2R)(AuPPh3)};]ClO4 (R &.dbnd; Me, Et).

NEUTRAL, CATIONIC AND ANIONIC 2-((PHENYLAZO)PHENYL) COMPLEXES OF GOLD(III)

Abstract [AuCl3(tht)] (tht = tetrahydrothiophene) reacts with [Hg(Az)Cl] [Az = 2-(phenylazo)phenyl, 2-(C6H4N=NC6H5)] in the presence of Me4NCl to give dichloro-2[(phenylazo)phenyl]gold(III), [Au(Az)Cl2]. By reacting this complex with neutral ligands, complexes of the types [Au(Az)Cl2L] (L = PPh3, PCy3, P(o-MeOC6H4)3, PBun3, AsPh3) and [(Az)Cl2Au(LL)AuCl2(Az)] (LL = Ph2P(CH2)2PPh2, dpe) have been obtained. Starting from [Au(Az)Cl2-(PCy3)] it is possible to substitute one or two chlorofor iodo- ligands to give complexes [Au(Az)ClI-(PCy3] and [Au(Az)I2(PCy3)]. Cationic complexes [Au(Az)ClLL′]ClO4 have been synthesized by reacting [Au(Az)Cl2] or the corresponding neutral complexes [Au(Az)ClL] with neutral monodentate (L = L′ PPh3, PCy3; L = PPh3, L′ = py, tht; L = PCy3, L′ = py) or bidentate ligands (LL′ = dpe, phen) and NaClO4. The reaction of [Au(Az)Cl2] with BzPh3PCl gives the anionic complex BzPh3P[Au(Az)Cl3].

Keto-stabilized phosphorus ylide gold (I) and gold (III) complexes

Abstract Reactions between [AuCl(tht)] (tht = tetrahydrothiophene) and the ylides Ph3PCHC(O)R give complexes [AuCl“CH(PPh3)C(O)R”] (R = Me, Ph), which react (1) with chlorine to give [AUCl3“CH(PPh3)C(O)R”] (R = Me, Ph) and (2) with the same ylide and NaClO4 to form [Au“CH(PPh3)C(O)R”2]ClO4 (R = Me, Ph). The latter species react with chlorine to give trans-[AuCl2“CH(PPh3)C(O)R”2]ClO4 (R = Me), and with [Au(acac)(PPh3)] (molar ratio 1 2 ) to give [Au“C(AuPPh3)-(PPh3)C(O)R”2]ClO4 (R = OMe, OEt). The phosphonium salts [Ph3PCH2C(O)R]-ClO4 react with [Au(acac)(EPh3)] (acac = acetylacetonate) in 1 1 or 1 2 molar ratio to give, respectively, [Au“CH(PPh3)C(O)R”(PPh3)]ClO4 (R = Me, Ph) or [“Au(EPh3)”2“μ-C(PPh3)C(O)R”]ClO4 (E = P, R = Me, Ph; E = As, R = Me).

Synthesis of mixed diarylgold(III) complexes. Crystal structure of cis-[2-(phenylazo)phenyl][2-{(dimethylamino)methyl}phenyl]gold(III) tetrachloroaurate

The reaction (1 : 1) between [Au(2-C6H4CH2NMe2)Cl2] and [Hg(2-C6H4-NNPh)2] gives the complex [(2-PhNNC6H4)Au(2-C6H4CH2NMeC2)Cl], which on treatment with AgClO4 gives [(2-PhNNC6H4)Au(2-C6H4CH2NMe2)]ClO4. From this complex, the species [(2-PhNNC6H4)Au(2-C6H4CH2NMe2)X] (X  CH3COO, CN), or [(2-PhNNC6H4)Au(2-C6H4CH2NMe2)L] (L  PPh3, py) are obtained by reaction with the corresponding KX salts or neutral ligands. The crystal structure of [(2-PhNNC6H4)Au(2-C6H4CH2NMe2)][AuCl4] (obtained by metathesis between the corresponding perchlorate and tetramethylammonium salts) has been determined; the cation displays square-planar coordination with two cis-nitrogen (AuN: 2.166(15), 2.140(14) A) and two cis-carbon (AuC: 2.021(16), 2.033(17) A) atoms bonded to the gold atom.

Synthesis and structural characterization of gold-(I), -(III) and silver(I) complexes of the ylide ligand Ph3PCHC(O)NMe2. Crystal structure of [(AuPPh3)2{µ-C(PPh3)C(O)NMe2}]ClO4

The reaction between [AuCl(tht)](tht = tetrahydrothiophene) and the ylide Ph3PCHC(O)NMe2 gives [AuCl{CH(PPh3)C(O)NMe2}]1, which reacts with chlorine to gives [AuCl3{CH(PPh3)C(O)NMe2}]2 and with the same ylide and NaClO4 to form [Au{CH(PPh3)C(O)NMe2}2]ClO43. The analogous silver complex [Ag{CH(PPh3)C(O)NMe2}2]ClO44 is obtained by the reaction of AgClO4 with the ylide in molar ratio 1 : 2. The phosphonium salt [Ph3PCH2C(O)NMe2]ClO4 reacts with [Au(acac)(PPh3)](acac = acetylacetonate) to gives [Au{CH(PPh3)C(O)NMe2}(PPh3)]ClO45 or [(AuPPh3)2{µ-C(PPh3)C(O)NMe2}]ClO46 depending on the reaction conditions. The structure of 6 was confirmed by an X-ray diffraction study at –95 °C [space group P, a= 11.572(3), b= 11.836(3), c= 21.627(7)A, α= 78.29(2), β= 87.19(2), γ= 75.65(2)°, R= 0.076]; the Au ⋯ Au bond length is 2.938(1)A.

A new way of synthesising diarylgold(III) complexes using organomercury compounds

Abstract Treatment of [Me 4 N][AuCl 4 ] with di-organomercury derivatives R 2 Hg in which R is an ortho -nitroaryl group (R = o -O 2 NC 6 H 4 or 2-CH 3 , 6-O 2 NC 6 H 3 ) gives anionic gold(III) complexes of the type cis -Me 4 N[AuR 2 Cl 2 ]. These react with (a) KCN, to give the anionic complexes cis -Me 4 N[AuR 2 (CN) 2 ], (b) neutral monodentate ligands (L) to give the neutral complexes cis -[AuR 2 Cl(L)] (L = PPh 3 , PCy 3 , py), and (c) 1,2-bis(diphenylphosphino)ethane (dpe) in the presence of NaClO 4 to give the cationic complexes cis -[AuR 2 (dpe)]ClO 4 . The complexes are thought to be the first transition metal complexes containing ortho -nitroaryl ligands.

C–H activation of acetone by 2-phenylazophenylgold(III) complexes; synthesis of the first acetonylgold(III) complex

The complex [A[graphic ommitted]Ph)(CH2COMe)Cl](1) can be obtained by the reaction of [A[graphic ommitted]Ph)Cl2] with Tl(acac)(acacH = acetylacetone) in acetone at room temperature, and at 0 °C the intermediate[A([graphic ommitted]Ph)(acac)Cl](2) can be isolated; this and other reactions that lead to complex (1), which is the first acetonylgold(III) complex, are the first examples of alkyl C–H activation by a gold(III) complex.

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.

ortho-, meta- and para-nitrophenylgold(I) complexes

Abstract Treatment of [BzPh 3 P][AuCl 2 ] with [Hg( x -C 6 H 4 NO 2 ) 2 ] ( x = o , m , or p ) gives anionic gold(I) complexes of the type [BzPh 3 P][Au(R)Cl](R = o -, m - or p -C 6 H 4 NO 2 , Bz = C 6 H 5 CH 2 ). The chloro ligand in [Au( o -C 6 H 4 NO 2 )Cl] − can be replaced by bromo or iodo ligands by use of NaBr or NaI. The anions [Au(R)Cl] − react with neutral monodentate ligands, L, to give neutral mononuclear complexes [Au(R)L] (R = o -C 6 H 4 NO 2 , L = PPh 3 , AsPh 3 ; R = m -C 6 H 4 NO 2 , L = PPh 3 ) and with 1,2-bis(diphenylphosphino)ethane (dpe) to give [Au 2 (R) 2 (dpe)] (R = o -C 6 H 4 NO 2 ). The corresponding [Au( p -C 6 H 4 NO 2 )Cl] − reacts with PPh 3 or AsPh 3 to give mixtures containing [AuClL]. The anionic ortho -nitrophenylgold(I) complex is much more stable than its meta - or para -nitrophenyl isomers. These are thought to be the first reports of nitrophenylgold(I) complexes.