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
摘要:
The reaction between [AuCl(tht)] (tht = tetrahydrothiophene) and the ylide Ph3P = CHC(O)NMe2 gives [AuCl{CH(PPh3)C(O)NMe2}] 1, which reacts with chlorine to give [AuCl3{CH(PPh3)C(O)-NMe2}] 2 and with the same ylide and NaClO4 to form [Au{CH(PPh3)C(O)NMe2}2]ClO4 3. The analogous silver complex [Ag{CH(PPh3)C(O)NMe2}2]ClO4 4 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 give [Au{CH(PPh3)C(O)NMe2}(PPh3)]ClO4 5 or [(AuPPh3)2{mu-C(PPh3)C(O)NMe2}]ClO4 6 depending on the reaction conditions. The structure of 6 was confirmed by an X-ray diffraction study at -95-degrees-C [space group P1BAR, a = 11.572(3), b = 11.836(3), c = 21.627(7) angstrom, alpha = 78.29(2), beta = 87.19(2), gamma = 75.65(2)-degrees, R = 0.076]; the Au...Au bond length is 2.938(1) angstrom.
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
摘要:
The reaction between [AuCl(tht)] (tht = tetrahydrothiophene) and the ylide Ph3P = CHC(O)NMe2 gives [AuCl{CH(PPh3)C(O)NMe2}] 1, which reacts with chlorine to give [AuCl3{CH(PPh3)C(O)-NMe2}] 2 and with the same ylide and NaClO4 to form [Au{CH(PPh3)C(O)NMe2}2]ClO4 3. The analogous silver complex [Ag{CH(PPh3)C(O)NMe2}2]ClO4 4 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 give [Au{CH(PPh3)C(O)NMe2}(PPh3)]ClO4 5 or [(AuPPh3)2{mu-C(PPh3)C(O)NMe2}]ClO4 6 depending on the reaction conditions. The structure of 6 was confirmed by an X-ray diffraction study at -95-degrees-C [space group P1BAR, a = 11.572(3), b = 11.836(3), c = 21.627(7) angstrom, alpha = 78.29(2), beta = 87.19(2), gamma = 75.65(2)-degrees, R = 0.076]; the Au...Au bond length is 2.938(1) angstrom.
No cycle required: The straightforward synthesis of acyclic (amino)(ylide)carbene gold complexes was achieved by reaction of isocyanide gold complexes with phosphorus and arsenic ylides as well as electron‐rich olefins. Their ability to form bimetallic species and to act as ligand‐transfer reagents has also been established.