112596-64-2Relevant articles and documents
Synthesis of gold(I), gold(III), and silver(I) complexes with ylide ligands derived from carbonylbis(methylenetriphenylphosphonium) diperchlorate. Crystal and molecular structures of [Au2{μ-{{CH(PPh3)}2CO}} 2](ClO4)2, [(Ph3PCCl2)2CO][AuCl4 ...
Vicente, Jose,Chicote, Maria-Teresa,Saura-Llamas, Isabel,Jones, Peter G.,Meyer-B?se, Karen,Erdbrügger, Cristina Freire
, p. 997 - 1006 (2008/10/08)
Full title: Synthesis of gold(I), gold(III), and silver(I) complexes with ylide ligands derived from carbonylbis(methylenetriphenylphosphonium) diperchlorate. Crystal and molecular structures of [Au2{μ-{{CH(PPh3)}2CO}} 2](ClO4)2, [(Ph3PCCl2)2CO][AuCl4](ClO 4), [(AuL)2{μ-{C(PPh3)C(O)CH(PPh 3)(AuL)}}](ClO4)2 (L = PPh3), and [{Au(PMe2Ph)}4{μ-{{C(PPh3)} 2CO}}](ClO4)2. Transylidation reactions between the diphosphonium salt [(Ph3PCH2)2CO](ClO4)2 and [M{CH-(PPh3)C(O)CH3}2]ClO4 (1:1) (M = Ag, Au) give [M2{μ-{{CH(PPh3)}2CO}}2](ClO 4)2 [M = Ag (1), Au (2)]. Complex 1 reacts with [AuCl(tht)] (1:1; tht = tetrahydrothiophene) to give 2. This complex reacts with an excess of chlorine to give trans-[(AuCl2)2{μ-{{CH(PPh3)} 2CO}}2](ClO4)2 (3), but slow diffusion of the reacting solutions into each other gives instead the new diphosphonium salt [(Ph3PCCl2)2CO][AuCl4](ClO 4) (3a). The diphosphonium salt [(Ph3PCH2)2CO](ClO4)2 reacts with [AuCl{CH(PPh3)C(O)CH3}] leading to an equilibrium between the starting compounds and the products of successive transylidation reactions, [AuCl{CH(PPh3)C(O)CH2PPh3}]ClO4 (4) and [(AuCl)2{μ-{{CH(PPh3)}2CO}}] (5). From the reaction mixture only 5 can be isolated as a pure compound. However, when the new ylide-phosphonium salt [Ph3PCHC(O)CH2PPh3]ClO4 is reacted with [AuCl(tht)], complex 4 can be isolated. It reacts with [AuCl{CH(PPh3)C(O)CH3}] (1:1) to give 5, which, in turn, reacts with chlorine to give the gold(III) complex [(AuCl3)2{μ-{{CH(PPh3)}2CO}}] (6). [Au(acac)L] (acac = acetylacetonate) reacts with the diphosphonium salt [(Ph3PCH2)2CO](ClO4)2 (molar ratio ≥ 4:1) to give complexes of the type [(AuL)2{μ-{C(PPh3)C(O)-CH(PPh 3)(AuL)}}](ClO4)2 [L = PPh3 (7)] or [(AuL)4{μ-{{C(PPh3)}2CO}}](ClO 4)2 [L = PhMe2P (8)]. Single-crystal X-ray structure determinations were performed for compounds 2, 3a, 7, and 8. Compound 2 possesses a central eight-membered ring with a short transannular Au?Au contact of 2.876 A?. Compound 3a, the nature of which was only revealed by the X-ray study, contains centrosymmetric [AuCl4]- anions, ClO4- anions, and the novel, highly chlorinated phosphonium ion [(Ph3PCCl2)2CO]2+. Compounds 7 and 8 contain triangular Au2C units (Au-Au = 2.86-3.01 A?) to which three-center bonding probably makes a significant contribution; further short Au?Au contacts are observed between the Au2 groups and gold atoms farther away (3.15-3.34 A?). The Au-C-CO-C-Au backbone of compound 7 is disordered over two positions (occupation factors of ca. 89 and 11%); only the gold atoms of the minor disorder component could be identified.
