Synthesis and Characterization of Sulfur-Ylide Complexes of Gold(I). Observance of Intermolecular Gold(I)-Gold(I) Interactions in Solution
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- 作者：Da-Fa Feng ; Shaw Shiah Tang ; C. W. Liu ; Ivan J. B. Lin ; Yuh-Sheng Wen ; and Ling-Kang Liu
- 刊名：Organometallics
- 出版年：1997
- 出版时间：March 4, 1997
- 年：1997
- 卷：16
- 期：5
- 页码：901 - 909
- 全文大小：361K
- 年卷期：v.16,no.5(March 4, 1997)
- ISSN：1520-6041
文摘
Under PTC/OH- (PTC = phase-transfercatalysis) conditions, the reaction ofAu2(dppm)Cl2(dppm = 1,1-bis(diphenylphosphino)methane) with[Me2S(O)NMe2]BF4produces a greenishluminescent compound[Au2(dppm)[(CH2)2S(O)NMe2]]BF4,1, and a colorless tetranuclearcompound[Au4(dppm)(Ph2PCHPPh2)[(
-CH)(CH2)S(O)NMe2]]BF4,2. Both compounds 1 and2 also can be synthesized from[Au4(dppm)(Ph2PCHPPh2)Cl3],3, which can be producedsimply by the reaction ofAu2(dppm)Cl2 with OH-in the presence of a PTC. ForAu2(dppe)Cl2(dppe = 1,2-bis(diphenylphosphino)ethane) andAu2(dmpm)Cl2 (dmpm =1,1-bis(dimethylphosphino)methane), only[Au2(dppe)[(CH2)2S(O)NMe2]]PF6,4, and[Au2(dmpm)[(CH2)2S(O)NMe2]]BF4, 5, areobtained as the major product, respectively. Compounds1-4 arecharacterized by single-crystal X-ray analyses. TwoC2-related cations of 1 are packed inarow with the intermolecular Au-Au distance (2.959 Å) shorter thanthe intramolecular Au-Au distance (2.984 Å). Compound 2 has one of the ylidecarbon atoms bridging two gold(I)atoms. The tetragold cluster of 3 is formed by anAu-C linkage between[ClAu(-Ph2PCH2PPh2)Au]+ and[ClAu(-Ph2PCHPPh2)AuCl]-.The digold cation of 4 is a nine-membereddimetallocycle. In acetonitrile solution, dimerization of1 and 5 through intermolecular Au-Au interaction occurs as evidenced by concentration-dependent absorptionspectroscopicstudies. Concentration-dependent absorption spectra of1 and 5 suggest that equilibriumsbetween the monomer and dimer exist with equilibrium constants of 33± 9 and 52 ± 7 M-1in acetonitrile, respectively. Digold(I) compounds1, 4, and 5 luminesce in the solidstate.
-CH)(CH2)S(O)NMe2]]BF4,2. Both compounds 1 and2 also can be synthesized from[Au4(dppm)(Ph2PCHPPh2)Cl3],3, which can be producedsimply by the reaction ofAu2(dppm)Cl2 with OH-in the presence of a PTC. ForAu2(dppe)Cl2(dppe = 1,2-bis(diphenylphosphino)ethane) andAu2(dmpm)Cl2 (dmpm =1,1-bis(dimethylphosphino)methane), only[Au2(dppe)[(CH2)2S(O)NMe2]]PF6,4, and[Au2(dmpm)[(CH2)2S(O)NMe2]]BF4, 5, areobtained as the major product, respectively. Compounds1-4 arecharacterized by single-crystal X-ray analyses. TwoC2-related cations of 1 are packed inarow with the intermolecular Au-Au distance (2.959 Å) shorter thanthe intramolecular Au-Au distance (2.984 Å). Compound 2 has one of the ylidecarbon atoms bridging two gold(I)atoms. The tetragold cluster of 3 is formed by anAu-C linkage between[ClAu(-Ph2PCH2PPh2)Au]+ and[ClAu(-Ph2PCHPPh2)AuCl]-.The digold cation of 4 is a nine-membereddimetallocycle. In acetonitrile solution, dimerization of1 and 5 through intermolecular Au-Au interaction occurs as evidenced by concentration-dependent absorptionspectroscopicstudies. Concentration-dependent absorption spectra of1 and 5 suggest that equilibriumsbetween the monomer and dimer exist with equilibrium constants of 33± 9 and 52 ± 7 M-1in acetonitrile, respectively. Digold(I) compounds1, 4, and 5 luminesce in the solidstate.