CN102850404A - 一种钴配合物及其合成方法 - Google Patents

一种钴配合物及其合成方法 Download PDF

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CN102850404A
CN102850404A CN2012103741904A CN201210374190A CN102850404A CN 102850404 A CN102850404 A CN 102850404A CN 2012103741904 A CN2012103741904 A CN 2012103741904A CN 201210374190 A CN201210374190 A CN 201210374190A CN 102850404 A CN102850404 A CN 102850404A
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罗梅
邱晶晶
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Abstract

一种新型乙二胺钴氮配合物，其化学式如下：

Description

一种钴配合物及其合成方法
一、技术领域
本发明涉及一种金属有机配位化合物（配合物）及其制备方法，特别涉及含氮的金属有机配合物及其制备方法，确切地说是一种乙二胺钴配合物及其合成方法。
二、         背景技术
Co-N配合物在生物化学、材料科学、催化化学等方面都有着广泛的应用前景[1-4]， 其作为催化剂可用于烯烃的环氧化反应，降冰烯的聚合反应，硼氢化反应等。[5-7]
参考文献：
[1] Fabelo, J.; Pasa?n, L.; Can?adillas-Delgado, F. S. Inorg. Chem. Des.,2008，8：3984。
[2] Manna, S.C.；Zangrando, E.; Ribas,J.; Chaudhuri, N.R. 1norg. Chim.Acta，2008，361：411。
[3] Sun, W.H. Hao, P.; Zhang, S.; Shi，Q. S.; Zuo, W.W.; Tang, X.B. Organometallics，2007，26：   2720。
[4] Miodragovic,D. U.;Mitic，D.M .; M iodragovic, Z.M.; Bogdanovic, G. A.; Vitnik，Z.J.; Vitorovic，M.D.; Radulovic, M.D.; Nastasijevic, B.J.; Juranic，I.O.; Andelkovic，K.K. Inorganica Chimica Acta，2008，361：865。
[5]Jin, Chun; Xue, Wan-hua; Meng, Shuang-ming; Guo, Yong, Ranliao Huaxue Xuebao, 2009,      
  37(5),635-640。
[6] Zhang, D.; Yue, Q.; Wang, J. Y; Weng, L. H. , Inorganic Chemistry Communications , 2009, 12(12), 1193-1196. 
[7] Sugi, Kiyoaki D.; Nagata, T.; Yamada, T.; Mukaiyama, T. Chemistry Letters, 1997, 6, 493-494.  
三、发明内容
本发明旨在提供一种Co-N金属有机配合物以应用于催化领域，所要解决的技术问题遴选乙二胺作为配体并合成乙二胺钴氮配合物
   本发明所称的乙二胺钴氮配合物一种是由乙二胺与四水合醋酸钴制备的由以下化学式所示的配合物：
（Ⅰ）
    化学名称：乙二胺合醋酸钴（Ⅱ）。下称乙二胺醋酸钴，简称配合物(I)。
   本配合物（I）的合成方法是乙二胺与四水合醋酸钴以摩尔比2:1进行反应，用无水乙醇做反应溶剂，回流搅拌反应15小时，热过滤，滤液旋干后，用无水乙醇和正己烷重结晶，一天后出现粉色晶体。
 
四、附图说明
图1是配合物 (I) 的单晶衍射图。
五、具体实施方式
1、乙二胺醋酸钴配合物（Ⅰ）的合成
称取四水合醋酸钴1.5428g(0.0062mol),乙二胺0.84mL (0.0124mol)于100mL圆底烧瓶中，加入30mL无水乙醇,搅拌回流15小时，热过滤，将滤液旋干后，用无水乙醇和正己烷重结晶，一天后出现粉色晶体。元素分析结果如下：C,31.39%;H,7.32%; N,14.51%.；IR( KBr) :3252，2966, 1581, 1380，1330, 1215，1130，570。
化合物的晶体结构测定：
   在显微镜下选取合适大小的单晶在室温下进行X-射线单晶衍射实验，在293k温度下，在Oxford X-射线单晶衍射仪上，用经石墨单色器单色化的MoKa射线（λ=0.71073 A）以w-Theta 扫描方式收集衍射数据。对所得数据进行Lp因子及经验吸收校正，晶体结构由直接法解出，衍射数据还原和结构解析工作分别使用SAINT-5.0和SHELXS-97程序完成。晶体数据如下：  
      Identification code               mo_dm11648_0m 
      Empirical formula                 C14 H37 Co N4 O8 
      Formula weight                    448.41 
      Temperature                       140(2) K 
      Wavelength                        0.71073 A 
      Crystal system, space group       Triclinic,  P-1 
      Unit cell dimensions              a = 8.6296(12) A   alpha = 75.335(2) deg. 
                                        b = 12.0291(17) A    beta = 69.991(2) deg. 
                                        c = 12.1108(17) A   gamma = 72.248(2) deg. 
      Volume                            1109.4(3) A^3 
      Z, Calculated density             2,  1.342 Mg/m^3 
      Absorption coefficient            0.817 mm^-1 
      F(000)                            480 
      Crystal size                      0.35 x 0.20 x 0.04 mm 
      Theta range for data collection   1.81 to 27.00 deg. 
       Limiting indices                  -11<=h<=10, -15<=k<=15, -15<=l<=15 
      Reflections collected / unique    8427 / 4817 [R(int) = 0.0182] 
      Completeness to theta = 27.00     99.5 % 
      Absorption correction             Semi-empirical from equivalents 
      Max. and min. transmission        0.9680 and 0.7630 
      Refinement method                 Full-matrix least-squares on F^2 
      Data / restraints / parameters    4817 / 1 / 254 
      Goodness-of-fit on F^2            1.039 
      Final R indices [I>2sigma(I)]     R1 = 0.0342, wR2 = 0.0928 
      R indices (all data)              R1 = 0.0430, wR2 = 0.0998 
      Largest diff. peak and hole       0.736 and -0.665 e.A^-3 
晶体典型的键长数据：
            Co(1)-O(1)#1                  1.9179(14) 
            Co(1)-O(1)                    1.9179(14) 
            Co(1)-N(1)#1                  1.9465(16) 
            Co(1)-N(1)                    1.9465(16) 
            Co(1)-N(2)#1                  1.9484(16) 
            Co(1)-N(2)                    1.9484(16) 
            Co(2)-O(5)#2                  1.9159(13) 
            Co(2)-O(5)                    1.9159(13) 
            Co(2)-N(4)#2                  1.9522(15) 
            Co(2)-N(4)                    1.9522(16) 
            Co(2)-N(3)                    1.9533(16) 
            Co(2)-N(3)#2                  1.9533(16) 
            O(1)-C(3)                     1.289(2) 
            O(2)-C(3)                     1.236(3) 
            O(3)-C(9)                     1.260(3) 
            O(4)-C(9)                     1.255(3) 
            O(5)-C(7)                     1.285(2) 
            O(6)-C(7)                     1.232(2) 
晶体典型的键角数据：
            O(1)#1-Co(1)-O(1)           180.0 
            O(1)#1-Co(1)-N(1)#1          92.48(7) 
            O(1)-Co(1)-N(1)#1            87.52(7) 
            O(1)#1-Co(1)-N(1)            87.52(7) 
            O(1)-Co(1)-N(1)              92.48(7) 
            N(1)#1-Co(1)-N(1)           180.0 
            O(1)#1-Co(1)-N(2)#1          84.43(7) 
            O(1)-Co(1)-N(2)#1            95.57(7) 
            N(1)#1-Co(1)-N(2)#1          86.06(7) 
            N(1)-Co(1)-N(2)#1            93.94(7) 
            O(1)#1-Co(1)-N(2)            95.57(7) 
            O(1)-Co(1)-N(2)              84.43(7) 
            N(1)#1-Co(1)-N(2)            93.94(7) 
            N(1)-Co(1)-N(2)              86.06(7) 
            N(2)#1-Co(1)-N(2)           180.0 
            O(5)#2-Co(2)-O(5)           180.000(1) 
            O(5)#2-Co(2)-N(4)#2          93.42(6) 
            O(5)-Co(2)-N(4)#2            86.58(6) 
            O(5)#2-Co(2)-N(4)            86.58(6) 
            O(5)-Co(2)-N(4)              93.42(6) 
            N(4)#2-Co(2)-N(4)           180.0 
            O(5)#2-Co(2)-N(3)            94.73(6) 
            O(5)-Co(2)-N(3)              85.27(6) 
            N(4)#2-Co(2)-N(3)            94.14(6) 
            N(4)-Co(2)-N(3)              85.86(6) 
            O(5)#2-Co(2)-N(3)#2          85.26(6) 
            O(5)-Co(2)-N(3)#2            94.74(6) 
            N(4)#2-Co(2)-N(3)#2          85.86(6) 
            N(4)-Co(2)-N(3)#2 。
。       
    2、腈硅化反应应用
2-苯基-2-（三甲硅氧基）丙腈的制备
Figure 976620DEST_PATH_IMAGE002
0.15mmol 配合物I , 苯甲醛0.1mL, TMSCN 0.3 mL (3.3mmol及2mL THF 相继在10~20?C下加入25mL 烧瓶中, 8h 后，加入水淬灭经柱层后（石油醚/二氯甲烷：5/1），得无色油状液体， 产率：90%，1H NMR (300MHz, CDCl3) 7.56–7.59 (m, 0.9 Hz, 2H), 7.31–7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H). 13C NMR (75 MHz, CDCl3) 136.1, 128.8(x2), 126.2(x2), 119.1, 63.5, -0.39(x3)。

Claims (2)

1.一种钴配合物及其合成方法，其特征在于：由乙二胺与四水合醋酸钴制备的、由以下化学式所示的配合物（I）：
                                    （Ⅰ）。
2.由权利要求1所述配合物(I)的合成方法，以乙二胺与四水合醋酸钴为原料，包括合成、分离、结晶和洗涤，其特征在于：乙二胺与四水合醋酸钴以摩尔比2:1进行反应，用无水乙醇做反应溶剂，搅拌回流反应15小时，热过滤，滤液旋干后，用无水乙醇和正己烷重结晶，一天后出现粉色晶体。
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US3647845A (en) * 1969-09-12 1972-03-07 John B Wilkes Stabilization of cobalt carbonyl compounds by azoxy-dentated ligands
US3787464A (en) * 1969-12-30 1974-01-22 Snam Progetti Process for the preparation of trivalent cobalt complexes
US3803192A (en) * 1969-12-30 1974-04-09 Snam Progetti Oxidation products of cobalt complexes,process for obtaining same and insertion process
CN102093427A (zh) * 2011-01-12 2011-06-15 罗梅 一种镍氮配合物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647845A (en) * 1969-09-12 1972-03-07 John B Wilkes Stabilization of cobalt carbonyl compounds by azoxy-dentated ligands
US3787464A (en) * 1969-12-30 1974-01-22 Snam Progetti Process for the preparation of trivalent cobalt complexes
US3803192A (en) * 1969-12-30 1974-04-09 Snam Progetti Oxidation products of cobalt complexes,process for obtaining same and insertion process
CN102093427A (zh) * 2011-01-12 2011-06-15 罗梅 一种镍氮配合物

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