Synthesis of [Au3I3+, [Au2AgI3+, and [Au2CuI3+ Loose Clusters

Abstract

(2-Pyridylmethy1)triarylphosphonium salts, [R3PCH2(py-2)]X (py = pyridyl-2) react (i) with AgX, in 1 : 1 or 2: 1 molar ratios, togiveN-coordinated complexes [AgX2(py-CH2PTo3-2)] [X = clod, To = C6H4Me-4 (I)] or [AgX~(py- CH2PTo3-2)2][ X = C104 (2a), CF3SO3 = TfO (2b)], respectively, or (ii) with [AuCl.(tht)] (n = 1 or 3, tht = tetrahydrothiophene) to afford [ R ~ P CH~ ( ~ ~ - ~ ) ] [AU(Cn =I , 1+,~ R] = Ph (Sa), To (Sb); n = 3, R = Ph (6a), To (6b)l or (iii) with Tl(acac) (l:l, acacH = acetylacetone, X = AuC12) or ppn[Au(acac)2] [2:1, ppn = bis(triphenylphosphoranylidene)ammonium] or [Au(acac)(PR;)] (1 :2) to yield the ylide complexes [AuCl(CH- = R’ = Ph (sa), R = To? R’ = C6H40Me-4 = pmp (9b)], respectively. Complex 1 reacts with PR’3 (1:l) to give [Ag(ClO4)2(PR’3)(py-CH2PTo3-2}[]R ’ = Ph (sa), pmp (3b)l. 3a reacts with [AuCl(tht)] (1:l) leading to [Au- (PPh3)(py-CH2PTo3-2)](C104)(24 ). Complex 9a reacts with AgN03 (1:l) to give [(AuPPh3)2(p-(C(PPh3)(py- 2))}(p-Ag(~2-02NO)(OC103(l)o))], which reacts with [AuCl(PPh3)] and NaC104.H20 (1:l:l) leading to [ (AUPP~~)~{~L-(C(PP~~)(~~-(~C)10)4))(2-A2UHP2P0( ~11 ~)). ]C omplexes 9a and 9b react with CuCl to give [(AuPR’~)~{~-(C(PR~)(~~-~)})[R( C=U RC’ ~=) P]h( (C1~2aO)~; R) = To, R’ = pmp (12b)], respectively. The X-ray crystal structures of 9b and 10.CH2ClrH20 at 178 K show that weak interactions between both Au centers occur [2,949( 1) and 3.078( 1) A, respectively]. The configuration of the N lone pair with respect to the Au2 moiety isantiin9bwhilesynin 1ObecausetwoAwAgweakinteractions [2.926(1),3.006(1) A] seemtoactasaconformationdetermining force.