YLIDE TRANSFER-REACTIONS USED FOR THE SYNTHESIS OF DINUCLEAR AND TRINUCLEAR GOLD COMPLEXES - X-RAY STRUCTURE OF [AU3(MU(2)-CH2PPH2CH2)2(PPH3)2]TCNQ (TCNQ = 7,7',8,8'-TETRACYANOQUINODIMETHANE)

Reactions of the dinuclear derivative [Au2(mu-CH2PPh2CH2)2] with [AuL2]ClO4 (L = PPh3, PPh2Me, tht) or Q[AuX2] (X = Cl, Q = N(PPh3)2; X = Br, Q = PPh3Bz), in a 1:2 molar ratio, proceed with partial transfer of the bis(ylide) ligand to afford the cationic or anionic derivatives [Au2(mu-CH2PPh2CH2)L2]ClO4 (L = PPh3, PPh2Me, tht) or Q[Au2(mu-CH2PPh2CH2)X2] (X = Cl, Q = N(PPh3)2; X = Br, Q = PPh3Bz), respectively. When [Au(PPh3)2]ClO4 is used and the reaction is performed in a 1:1 molar ratio, the trinuclear derivative [Au3(mu2-CH2PPh2CH2)2(PPh3)2]ClO4 is obtained. Complexes [Au2(mu-CH2PPh2CH2)L2]ClO4(L=PPh3, tht) can be also obtained by reaction of Q[Au2(mu-CH2PPh2CH2)X2] (X = Cl, Br) with [Ag(OClO3)L] (L = PPh3, tht), and the anionic derivative [N(PPh3)2][AU2(mu-CH2PPh2CH2)Cl2] undergoes oxidative addition of chlorine to give the gold(II) compound [N(PPh3)2] [Au2(mu-CH2PPh2CH2)Cl4]. The structure of [Au3(mu2-CH2PPh2CH2)2(PPh3)2]TCNQ has been determined by a single-crystal X-ray diffraction study. It crystallizes in the space group P1BAR with a = 12.221(3) angstrom, b = 13.220(3) angstrom, c = 22.690(5) angstrom, alpha = 98-12(2)degrees, beta = 91.39(2)degrees, gamma = 115.76(2)degrees, Z = 2 (at-95-degrees-C). Intramolecular Au...Au contacts of 3.391 and 3.544 angstrom are observed.