含氮,磷雙牙混合配子VIB金屬錯合物的合成及結構研究-[Mo(CO)3(phen))2(μ-dppp)],[Mo(CO)3(N-N)(dppm)](N-N=phen,bipy,bpp)

• Main Author: 施育堯
• Other Authors: 翁春和
• Format: Others
• Language: zh-TW
• Published: 1994
• Online Access: http://ndltd.ncl.edu.tw/handle/80149682374439085204

碩士 === 國立臺灣師範大學 === 化學學系 === 82 === 　　Molybdenum tricarbonyl complexes containing nitrogen and phosphorous ligands were synthesized with Mo(CO)4(bipy), Mo(CO)4(phen), Mo(CO)4(bpp) (bpp=2, 3-Bis(2-pyridyl)pyrazine) and alkyl-bis(diphenyl phosphino) ligand by oxidative decarbonylation using trimethylamine N-oxide as an chemical initiator. complexes were indentified by nfrared and other spectra. The crystal structures of Cr(CO)4(72-bpp)(1), Mo(CO)4(72-bpp)(2), Mo(CO)3(bipy)(71-dppm)(3), W(CO)4(72-tpy)(4), {Mo(CO)3(phen)}2(μ-dppm)(5), Mo(CO)3(phen)(71-dppm)(6), Mo(CO)3(72-bpp)(71-dppm)(7) have been undertaken by X-ray diffration method. 　　Browm red crystal of 1 crystallized in the monoclinic space group P 21/n with a=12.220(6)A, b=11.607(6)A, c=13.076(5)A, β=112.18(4)°, V=1717.5(1)A3, Z=4, Rf=0.050, Rw=0.059, Gof=3.82. 　　Browm red crystal of 2 crystallized in the monoclinic space group P 21/n with a=12.364(3)A, b=11.5253(2)A, c=13.314(7)A, β=112.86(3)°, V=1748.2(1)A3, Z=4, final R value are Rf=0.033, Rw=0.030, Gof=1.73; crystal 2 and crystal 1 are isomorphous. 　　Deeply red crystal of 3 crystallized in the monoclinic space group C 2/c with a=28.081(7)A, b=10.698(8)A, c=22.893(6)A, β=101.852(2)°, V=6731(6)A3, Z=8, final R value are Rf=0.052, Rw=0.047, Gof=2.05. 　　Browm red crystal of 4 crystallized in the triclinic space group P 1 with a=7.190(3)A, b=11.062(3)A, c=13.447(4)A, α=102.47(3)°, β=89.762(3)°, γ=102.27(3)°, V=1019.5(6)A3, Z=2, Rf=0.082, Rw=0.130, Gof=8.11. 　　Deeply red crystal of 5 crystallized in the monoclinic space group P 21/c with a=10.7743(2)A, b=26.297(3)A, c=18.921(5)A, β=100.740(2)°, V=5267.0(17)A3, Z=4, final R value are Rf=0.055, Rw=0.050, Gof=1.76. 　　Deeply red crystal of 6 crystallized in the monoclinic space group P 21/n with a=18.429(6)A, b=11.1618(2)A, c=20.189(4)A, β=107.395(2)°, V=3962.9(2)A3, Z=4, final R value are Rf=0.098, Rw=0.093, Gof=4.00. 　　Blue green crystal of 7 crystallized in the trigonal space group R 3 with a=28.589(6), c=29.261(1)A, V=20712(8)A3, Z=18, Rf=0.094, Rw=0.113, Gof=4.16；complexes (7), (6) and (3) are similiar with that the bidentate (P-P) ligand uses only one phosphine to coordinate to metal, and the other phosphine atom in the same ligand is dangling.