含多芽氮配位基與過渡金屬化合物之化學研究

本論文主要探討含多芽氮配位基與過渡金屬化合物的化學。以Mo2(DpyF)4為起始物，加入過量的HBF4在CH3CN中反應，可得到化合物cis-[Mo2(HDpyF)2(CH3CN)4][BF4]4，1，將此化合物加入溶劑砒碇反應，可得到化合物trans-[Mo2(DpyF)2(py)4][BF4]2 ，2。以上兩種產物皆經過UV-vis和1H-NMR的測定，而且兩者的結構都已確定。化合物1的空間群為Cmca，a = 38.003(3) Å，b = 12.847(2) Å，c = 22.023(2) Å，V = 10752(2) Å3，Z = 8，R1 = 0.0504，wR2 = 0.1454，兩個HDpyF配位基以橋接的型式鍵結到金屬原子上，而且胺基上的氫原子與雙鉬金屬形成agostic作用力。化合物2的空間群為P21/n，a = 10.920(1) Å，b = 14.162(1) Å，c = 17.012(1) Å，β = 99.378(1) a，V = 2595.8(2) Å3，Z = 2，R1 = 0.0443，wR2 = 0.1029。另一方面以HDMpyF(HDMpyF = N,N’-di(2-(6-methyl-pyridyl)formamidine)配位基與MnCl2反應可以得到不同於MnCl(HDpyF)配位模式的化合物MnCl2(HDMpyF)2，3，並且結構已被鑑定。化合物3的空間群為C2/c，a = 23.719(2) Å，b = 11.548(1) Å，c = 14.342(1) Å，β = 124.071(2)a，V = 3253.8(5) Å3，Z = 1，R1 = 0.0508，wR2 = 0.1356。含砒碇環雙芽氮配位基的化合物M2(dppap)4(M = Cr，4；Mo，5) (Hdppap = 2-(diphenylphosphinoamino)pyridine)可由CrCl2與Mo2(O2CCH3)4為起始物，分別和二當量及四當量的Hdppap的陰離子在THF中反應合成出。將Mo2(dppap)4溶於THF並與hexanes在空氣下擴散養晶可得到化合物Mo2O2(dppap)4，6。另外，以[Cu(CH3CN)4][PF6]和Hdppap在CH2Cl2下反應可得到化合物[Cu(HDppap)2][PF6]，7，這些化合物的UV-vis光譜、NMR及元素分析已被紀錄下來。化合物4、6及7的結構已被鑑定。化合物4的空間群為Pī， a = 10.321(1) Å，b = 11.991(1) Å， c = 13.813(1) Å， α = 101.235(1) a， = 99.821(1) a，γ = 94.478(1) a， V = 1641.0(2) Å3， Z = 1，R1 = 0.0522，wR2 = 0.1399，Cr-Cr鍵長為1.8866(9) Å，是在超短的四重鍵長範圍之內。化合物6的空間群為C2/c，a = 21.117(1) Å，b =17.617(1) Å，c = 20.435(1) Å，β = 93.595(1)a，V = 7587.4(7) Å3，Z = 4，R1 = 0.0480，wR2 = 0.1089。化合物7的空間群為C2， a = 15.653(1) Å，b = 11.883(1)， c = 12.335(1) Å， = 121.578(6) a， V = 1954.6(3) Å3， Z = 2，R1 = 0.0491，wR2 = 0.1413。

關鍵字

多芽氮配位基；過渡金屬化合物

並列摘要

The complex cis-[Mo2(HDpyF)2(CH3CN)4][BF4]4, 1, was prepared by reaction of Mo2(DpyF)4 with excess HBF4 in THF. The reactions of 1 with pyridine afforded the complex trans-[Mo2(DpyF)2(py)4][BF4]2, 2. Their UV-vis and 1H-NMR spectra have been recorded and their structures have been determined. Crystal data for 1: space group Cmca, a = 38.003(3) Å, b = 12.847(2) Å, c = 22.023(2) Å, V = 10752(2) Å3, Z = 8, with final residuals R1 = 0.0504 and wR2 = 0.1454. The two Mo atoms are bridged by two HDpyF neutral ligands. The amine groups of the two HDpyF ligands lie close to and interact with the Mo atoms, giving rise to two N-H---Mo(II) agostic interactions. Crystal data for 2: space group P21/n, a = 10.920(1) Å, b = 14.162(1) Å, c = 17.012(1) Å, β = 99.378(1) a, V = 2595.8(2) Å3, Z = 2, with final residuals R1 = 0.0443, wR2 = 0.1029. Reaction of MnCl2 with HDMpyF afforded the complex MnCl2(HDMpyF)2, 3. Crystal data for 3: space group C2/c, a = 23.719(2) Å, b = 11.548(1) Å, c = 14.342(1) Å, β = 124.07(1)a, V = 3253.8(5) Å3, Z = 1, with final residuals R1 = 0.0508, wR2 = 0.1356。 The compounds M2(dppap)(M = Cr, 4; Mo, 5) were prepared by reaction of CrCl2 and Mo2(O2CCH3)4, respectively, with lithium salt of Hdppap (Hdppap = 2-(diphenylphosphinoamino)pyridine) in THF. The complex Mo2O2(dppap)4, 6, was prepared by dissolving complex 5 in THF, and layered with hexanes in air. Reaction of [Cu(CH3CN)4][PF6] with Hdppap in CH2Cl2 afforded the complex [Cu(HDppap)2][PF6], 7. These compounds have been characterized by analytical and spectroscopic data. The structures of 4, 6 and 7 have been determined by X-ray crystallography. Crystal data for 4 : space group Pī, a = 10.321(1) Å, b = 11.991(1) Å, c = 13.813(1) Å, α = 101.235(1) a, = 99.821(1) a, γ = 94.478(1) a, V = 1641.0(2) Å3, Z = 1, with final residuals R1 = 0.0522, wR2 = 0.1399. The Cr-Cr distance is 1.8866(9) Å which indicates a supershort quadruple bond. Crystal data for 6 : space group C2/c, a = 21.117(1) Å, b =17.617(1) Å, c = 20.435(1) Å, β = 93.595(1)a, V = 7587.4(7) Å3, Z = 4, with final residuals R1 = 0.0480, wR2 = 0.1089. Crystal data for 7 : space group C2, a = 15.653(1) Å, b = 11.883(1), c = 12.335(1) Å, = 121.578(6) a, V = 1954.6(3) Å3, Z = 2, with final residuals R1 = 0.0491，wR2 = 0.1413.

並列關鍵字

Transition Metal Complexes ； Polydentate Nitrogen Ligands

參考文獻

14. Cotton, F. A.; Daniels, L. M.; Murillo, C. A.; Wang, X. Chem. Commun., 1998, 39.

31. Cotton, F. A.; Daniels, L. M.; Lei, P.; Murillo, C. A.; Wang, X. Inorg. Chem., 2001, in print.

2. Cotton, F. A.; Daniels, L. M.; Murillo, C. A. J. Chem. Soc., Dalton Trans., 1998, 3151.

6. Cotton, F. A.; Lin, C.; Murillo, C. A. J. Am. Chem. Soc., 2001, 2670.

9. Cotton, F. A.; Ren, T. J. Am. Chem. Soc., 1992, 114, 2237.

國際替代計量

含多芽氮配位基與過渡金屬化合物之化學研究

未授權

主題瀏覽