- 作者: 林英智、易光輝、李錦祥、黃守齡、王瑜
- 作者服務機構: Department of Applied Cosmetology, Hungkuang University, Shalu, Taichung, Taiwan 433, R.O.C.
- 中文摘要: Treatment of Pd(PPh3)4 with N,N-dimethylthiocarbamoyl chloride, Me2NC(=S)Cl, in dichloromethane at -20 °C produces complex [Pd(PPh3)2(01-SCNMe2)(Cl)] (1). In solution state, complex 1 shows the intramolecular dissociation of the chloride or intermolecular dissociation of the triphenylphosphine ligands to form 02-thiocarbamoyl complex [Pd(PPh3)2(02-SCNMe2)][Cl] (2) or the bridging 02-thiocarbamoyl dipalladium complex [Pd(PPh3)Cl]2(μ,02-SCNMe2)2 (3). Treatment of 1 with MeOCS2K yields [Pd(PPh3){01-C(Sme)(NMe2)}(02-S2CO)] (5a). The Fischer-type carbene-complex 5a is formed via methyl migration of the methyldithiocarbonate to thiocarbamoyl ligand. Complex 1 reacts with EtOCS2K resulting in the formation of 02-dithiocarbonate complex [Pd(PPh3)(01-SCNMe2)(02-S2COEt)] (4b) and carbene-complex [Pd(PPh3){01-C(Set)(NMe2)}(02-S2CO)] (5b) with ratios of 10:1 from the integration of 31P{1H} NMR spectra. By continuously stirring the mixtures 4b and 5b in CH2Cl2 solution for 2 h, complex 5b was formed as the final product. Complex [Pd(01-SCNMe2)(02-Phen)(Cl)] (6) or [Pd{01-SC(O)NMe2}Pd(Cl)](μ,02-SCNMe2)- (μ,02-dppm)2 (7) is accessible by the reaction of 1 with phen (1,10-phenanthroline) or dppm {bis(diphenylphosphino)methane} in dichloromethane at room temperature. All of the complexes are identified by spectroscopic methods and complexes 1, 3, 5a, and 7 are determined by single-crystal X-ray diffraction. The complexes 1 and 3 crystallize in the monoclinic space group P21/n and P21/c with Z = 4, respectively, whereas 5a and 7 belong to the triclinic space group P with Z = 2. The cell dimensions are as follows: for 1, a = 12.8248(1) A, b = 18.6358(2) A, c = 14.9692(1) A, b = 105.1513(4)E; for 3, a = 9.8782(1) A, b = 11.7238(1) A, c = 20.7353(2) A, α = 103.9126(5)E, β = 97.8453(3)E, ( = 104.9669(5)E; for 5a, a = 16.3638(2) A, b = 9.3374(1) A, c = 15.7117(2) A, β = 98.2957(6)E; for 7, a = 12.1128(1) A, b = 14.0133(2) A, c = 17.7873(2) A, α = 82.1939(5), β = 79.6190(6)E, ( = 80.9551(5)E.
- 英文摘要: --
- 中文關鍵字: N,N-dimethylthiocarbamoyl chloride; Intramolecular intermolecular dissociation; 02-thiocarbamoyl; Fischer-type carbene; Methyl migration; Palladium complex.
- 英文關鍵字: --