Syntheses and Crystal Structures of Metal Complexes Containing Hexadentate Phosphine Ligands

• Main Author: 賴政國
• Other Authors: 翁春和
• Format: Others
• Language: zh-TW
• Published: 1999
• Online Access: http://ndltd.ncl.edu.tw/handle/53837506031015468446

博士 === 國立臺灣師範大學 === 化學學系 === 87 === Treatments of [Fe2(CO)4(η5-C5H5)2] with diphosphine ligands, Ph2P-(CH2)nPPh2 (n=1, dppm; n=2, dppe; and n=3, dppp), via thermoiyticmethod afford four disubstituted compounds: [{Fe(CO)(η5-C5H5)}2dppm](1), [{Fe(CO)(η5-C5H5)}2dppe](2), [{Fe(CO)(η5-C5H5)}2dppp](3) and[{Fe(η5-C5H5)C1}dppp](4). The reactions of [Ir4(CO)12] with{Fe(C5H4PPh2)2}(dppf) by thermolytic method yield five compounds:[HIr4(CO)7{Fe(C5H4PPh2)2}{Fe(C5H4PPh2)(C5H3PPh2)}](5), [H2Ir4(CO)6-{Fe(C5H4PPh2)(C5H3PPh2)}2](6), [H3Ir4(CO)4{Fe(C5H4PPh2)(C5H3PPh2)}-{Fe(C5H4)(C5H4P(Ph)(C6H4)}{P(Ph)(C6H4)}](7), [H4Ir4(CO)4{Fe(C5H3PPh2)-(C5H4P(Ph)(C6H4)}2](8) and [Ir4(CO)8(dppf)2](9). By chemical oxidation and thermoiytic methods, the reactions of M(CO)6(M: Cr, Mo, W) and NiX2(X: C1, Br, I) with hexadentate phosphine ligands [(Ph2PC2CH2)2P(CH2)2P(CH2CH2PPh2)2(P2(-Pf)4) and [(Ph2PCH2CH2)2P(CH2)3P(CH2CH2PPH2)2](P2(-Pf)4''), yield nine compounds: [{W(CO)5}6P2(-Pf)4](10), [{Cr(CO)3}2P2(-Pf)4](ll), [{Mo(CO)3}2- P2(-Pf)4''](12), [(NiC1)2P2(-Pf)4][PF6]2(13), [(NiC1)2P2(-Pf)4''][PF6]2(14), [(NiBr2)2P2(-Pf)4](15), [(NiBr)(NiBr2)P2(-Pf)4][PF6](16), [(NiBr)2-P2(-Pf)4[PF6]2(17) and [(NiI2)2P2(-Pf)4''](18). All compounds except (9) have been characterized by X-ray diffraction method and their crystal data are listed on Table 0.1.