Syntheses and Characterizations of Early Transition Metals Organohydroborate Complexes

• Main Authors: Jung-Hua Chen, 陳榮華
• Other Authors: Dean-Kuo Hsieh
• Format: Others
• Language: zh-TW
• Published: 2003
• Online Access: http://ndltd.ncl.edu.tw/handle/6x7a42

碩士 === 朝陽科技大學 === 應用化學系碩士班 === 91 === This dissertation separates two parts: The one synthesize methly and benzenely hydroborate complex, the other one synthesize cyanoborohydridely complexes. First, synthesize methly and benzenely hydroborate complex: take 4.50 mmol of PhB(OH)2 and 6.75 mmol of LiAlH4, and then, put them together in Ether, after that, we can get Li[H3BPh]。Otherwise, take 1.00 mmol of CpZrCl3 and 3.00 mmol of Li[H3BPh] together in Benzene, we can get CpZr{(μ-H)3BPh}3,（1）。Take 4.50 mmol of CH3B(OH)2 and 6.75 mmol of LiAlH4 together in Ether, then get the Li[H3BCH3]。Otherwise, take 1.00 mmol of CpZrCl3 and 3.00 mmol of Li[H3BCH3] together in the Benzene, we can get the CpZr{(μ-H)3BCH3}3, ( 2 )。Take 1.00 mmol of ZrCl4 and 4.00 mmol of Li[H3BPh] together in the Benzene, get the Zr{(μ-H)3B- Ph}4, ( 3 )。 Second, synthesize of cyanoborohydridely complexes: Take 1.00 mmol of Mo(CO)6 and CH3CN in 90℃ of the oil of the pot, we can get Mo(CO)3(NCCH3)3。Take 1.00 mmol of Mo(CO)3(NCCH3)3 and 1.00 mmol of C3H5Br together in the CH3CN，we can get the Mo(CO)2(NCCH3)2- (C3H5)(Br)。Next take 1.00 mmol of Mo(CO)2(NCCH3)2(C3H5)(Br) and 1.00 mmol of NaBH3CN in the CH3CN solution, we can get the Mo(CO)2(NCCH3) 2(C3H5)(NCBH3), ( 4 )。Take 1.00 mmol of W(CO)6 and CH3CN together in 90℃ of the oil of the pot, and then we can get the W(CO)3(NCCH3)3。Take 1.00 mmol of W(CO)3(NCCH3)3 and 1.00 mmol of C3H5Br together in the CH3CN solution, we can get the W(CO)2(NCCH3- )2(C3H5)(Br)。Next, take1.00 mmol of W(CO)2(NCCH3)2(C3H5)(Br) and 1.00 mmol of NaBH3CN together in the CH3CN solution, we can get the W(CO)2(NCCH3)2(C3H5)(NCBH3), ( 5 )。Used 1.00 mmol of Mo(CO)2(NCCH3)2(C3H5)(Br), and 3.00 mmol of NaBH3CN together in the CH3CN, we can get the [Na]2[Mo(CO)2(C3H5)(NCBH3)3]。Next, plus the 2.00 mmol of N(CH3)4Cl in the CH3CN solution, and then, used the hexane/DME having two layers solution to grow crystal, we can get the [N(CH3)4]2[Mo(CO)2(C3H5)(NCBH3)3]．1/2(C4H10O2), ( 6 )。Take the 1.00 mmol of W(CO)2(NCCH3)2(C3H5)(Br) and 3.00 mmol of NaBH3CN together in the CH3CN, we can get the[Na]2[W(CO)2(C3H5)(NCBH3)3]。Next, plus the 2.00 mmol N(CH3)4Cl to make a cation exchang reaction, in the hexane/DME having two layers solution to grow crystal, we can get the [N(CH3)4]2[W(CO)2(C3H5)(NCBH3)3]．1/2(C4H10O2), ( 7 )。Take 1.00 mmol of Cp2TiCl2 and 2.00 mmol of NaBH3CN together in the THF, we can get the Cp2Ti(NCBH3)(THF)．(THF), ( 8 )。Take 1.00 mmol of CpTiCl3 and 3.00 mmol of NaBH3CN together in the THF, we can get the [Na(THF)6][CpTi(NCBH3)4(THF)], ( 9 )。Take 1.00 mmol of CpTiCl3 and 6.00 mmol of NaBH3CN together in the THF, we can get the [Cp2Ti2(NCBH3)4][Ti(THF)4], ( 10 )。 Used the IR、11B、1H、X-ray and Anal. Calcd above the chemical compound, and probe into the organohydroborately and cyanoborohydridely of transition-metals bonding modes。