Heterocyclic Thionates as a New Class of Bridging Ligands in Oxo-Centered Triangular Cyclopentadienylchromium(III) Complexes
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- 作者：Victor Wee Lin Ng ; Seah Ling Kuan ; Weng Kee Leong ; Lip Lin Koh ; Geok Kheng Tan ; Lai Yoong Goh ; and Richard D. Webster
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：July 25, 2005
- 年：2005
- 卷：44
- 期：15
- 页码：5229 - 5240
- 全文大小：285K
- 年卷期：v.44,no.15(July 25, 2005)
- ISSN：1520-510X
文摘
The interactions of the benzothiazolate complex, CpCr(CO)2(SCSN(C6H4)) (2), and the tetrazole thiolate complex,CpCr(CO)3(
1-SCN4Ph) (3), with controlled amounts of Me3OBF4 and (MeO)2SO2, respectively, produced thecorresponding 
3-oxo trinuclear thionate-bridged complexes, [Cp3Cr3(2-OH)(3-O)(2-2-SCSN(C6H4))2](5)BF4 (45%)and [Cp3Cr3(2-OH)(3-O)(2-2-SCN4Ph)2](9)(MeOSO3) (53%), together with their respective free dimethylatedthiolate ligands, [MeSCSNMe(C6H4)](4)BF4 and (Me2SCN4Ph)(8)MeOSO3. The reaction of 3 with Me3OBF4 resultedin the isolation of a binuclear complex, [Cp2Cr2(-OH)(-2-SCN4Ph)2](7)BF4 (43%), and (8)BF4 (27%). The reactionof the thiopyridine complex, CpCr(CO)2(SPy) (4), with I2 also produced a similar 3-oxo complex 10 (31%), togetherwith CpCrI2(THF) (11) and the disulfide (SPy)2. Similar reactions with 2 and 3 and I2 yielded species 5 and 7,together with 11 and disulfides derived from their respective ligands. Cyclic voltammograms recorded in solutionsof 5 and 9 indicated that the compounds could be reduced and oxidized at very similar potentials. An EPR spectrumcharacteristic of a compound with axial symmetry was obtained for 9 at 7 K. Single-crystal X-ray diffraction analysesconfirmed that species 7 is dinuclear, whereas 5 and 9 are structural trinuclear analogues, each containing a3-oxo central core.
1-SCN4Ph) (3), with controlled amounts of Me3OBF4 and (MeO)2SO2, respectively, produced thecorresponding 3-oxo trinuclear thionate-bridged complexes, [Cp3Cr3(2-OH)(3-O)(2-2-SCSN(C6H4))2](5)BF4 (45%)and [Cp3Cr3(2-OH)(3-O)(2-2-SCN4Ph)2](9)(MeOSO3) (53%), together with their respective free dimethylatedthiolate ligands, [MeSCSNMe(C6H4)](4)BF4 and (Me2SCN4Ph)(8)MeOSO3. The reaction of 3 with Me3OBF4 resultedin the isolation of a binuclear complex, [Cp2Cr2(-OH)(-2-SCN4Ph)2](7)BF4 (43%), and (8)BF4 (27%). The reactionof the thiopyridine complex, CpCr(CO)2(SPy) (4), with I2 also produced a similar 3-oxo complex 10 (31%), togetherwith CpCrI2(THF) (11) and the disulfide (SPy)2. Similar reactions with 2 and 3 and I2 yielded species 5 and 7,together with 11 and disulfides derived from their respective ligands. Cyclic voltammograms recorded in solutionsof 5 and 9 indicated that the compounds could be reduced and oxidized at very similar potentials. An EPR spectrumcharacteristic of a compound with axial symmetry was obtained for 9 at 7 K. Single-crystal X-ray diffraction analysesconfirmed that species 7 is dinuclear, whereas 5 and 9 are structural trinuclear analogues, each containing a3-oxo central core.