多胺合钴氧合配合物的制备、表征和性能研究
摘要
氧载体是一类重要的过渡金属配合物。生物体利用体内的氧载体传递与贮存氧气。小分子模型化合物的研究对揭示氧载体在生物体内的作用具有重要的意义。在军事工业及民用事业中涉及诸如储氧、除氧、控制氧气浓度(如金属防腐、瓜果保鲜、人工血液等)等要求时，氧载体也发挥重要的作用。
近年来，固相反应在配位化学反应方面显示了极大的优越性，它突破传统液相反应的规律，可以获得一些在溶液中不能得到的物质。因此本文将固相反应引入到氧载体过渡金属配合物的研究中，以期有新的突破。为此，用惰性气氛下的液-固反应和在真空条件下的气-固反应这两种室温固相法分别去合成了配合物；同时，用同样的反应物进行非水溶剂液相合成，以期对比。全文共分六章。
1．评述了氧载体研究的近期发展，对一些典型的氧载体的结构和性质做了简要介绍，阐明了氧载体的研究意义及其应用。
2．以丙二胺、丁二胺、二丙三胺为配体与无水氯化钴及六水合氯化钴进行惰性气氛下的液-固反应、在真空条件下的气-固反应、非水溶剂液相合成。探讨了配位水对液-固反应配合物氧合性能的影响。
3．以上述三种多胺为配体与无水硫酸钴及七水合硫酸钴进行惰性气氛下的液-固反应、在真空条件下的气-固反应、非水溶剂液相合成。探讨了硫酸钴配合物的氧合性能。
4．以上述三种多胺为配体与四水合醋酸钻进行惰性气氛下的液－固
反应、在真空条件下的气－固反应、非水溶剂液相合成。发现不同胺的
产物的氧合性能不同。
5．以上述三种多胺为配体与六水合硝酸钻进行惰性气氛下的液－固
反应、在真空条件下的气－固反应、非水溶剂液相合成。本章依据以上
四章的结果，探讨了阴离于对氧载体氧合性能的影响。
6 提出了一个用活性纳米MnO。作氧化剂合成2，6一H甲酚基对
甲苯酚的新方法。
Oxygen carriers are certain important transition metal complexes which can transport and store dioxygen reversibly in living bodies. The study on oxygen carriers is of important significance in military and civil applications, especially in the fields of dioxygen separation, metal anti-corrosion and keeping Suits fresh.
Recently, solid-state reaction shows its great advantages in coordination chemistry. It breaks through rules of traditional liquid phase reaction and certain products can only be prepared by solid-state reactioa So introduction of solid-state reaction into the research of transition metal complexes of oxygen carriers would get a new break To establish this view, we have used solid-state reaction method to prepare some cobalt complexes as oxygen carriers, to study their oxygenation properties and to compare them with those obtained from classic liquid phase methods. The contents of this work contain six parts:
1. Recent development of oxygenation of cobalt complexes was reviewed, such as the structure and properties of some typical oxygen carriers. Their significance as model of natural oxygen carriers and potential applications in industrial processes were discussed..
2. A series of cobalt complexes were prepared from 1,3-diaminopropane , 1,4-diamino-butane, 3,3'-diaminodipropylamine with cobalt(II) chloride anhydrous, cobah(II) chloride hexahydrate via liquid-solid reaction , gas-solid reaction in room temperature and non-aqueous solution reactioa The influence of coordinated water to oxygenating properties of the complexes prepared by liquid-solid reaction was discussed.
3. A series of cobalt complexes were prepared from the three amines mentioned above and cobalt (II) sulfate anhydrous, cobalt (II) sulfate heptahydrate by the three
preparing ways above. The influence of coordinated water to oxygenating properties of the complexes prepared by liquid-solid reaction was discussed
4. Cobalt complexes were prepared from the three amines above and cobalt (II) acetate tetrahydrate by the three ways above. The result showed that complexes prepared by different amines have different oxygenating properties.
5. Cobalt complexes were prepared from the three amines above and cobak (II) nitrate hexahydrate by the three ways above. The influence of anion to the ability of oxygen carriers was discussed.
6. A new method of the preparation of 2,6-diformyl-4-methylphenol was presented Nanophase MnO2 was prepared and used in the synthesis of 2,6-diformyl-4-methylphenol.
近年来，固相反应在配位化学反应方面显示了极大的优越性，它突破传统液相反应的规律，可以获得一些在溶液中不能得到的物质。因此本文将固相反应引入到氧载体过渡金属配合物的研究中，以期有新的突破。为此，用惰性气氛下的液-固反应和在真空条件下的气-固反应这两种室温固相法分别去合成了配合物；同时，用同样的反应物进行非水溶剂液相合成，以期对比。全文共分六章。
1．评述了氧载体研究的近期发展，对一些典型的氧载体的结构和性质做了简要介绍，阐明了氧载体的研究意义及其应用。
2．以丙二胺、丁二胺、二丙三胺为配体与无水氯化钴及六水合氯化钴进行惰性气氛下的液-固反应、在真空条件下的气-固反应、非水溶剂液相合成。探讨了配位水对液-固反应配合物氧合性能的影响。
3．以上述三种多胺为配体与无水硫酸钴及七水合硫酸钴进行惰性气氛下的液-固反应、在真空条件下的气-固反应、非水溶剂液相合成。探讨了硫酸钴配合物的氧合性能。
4．以上述三种多胺为配体与四水合醋酸钻进行惰性气氛下的液－固
反应、在真空条件下的气－固反应、非水溶剂液相合成。发现不同胺的
产物的氧合性能不同。
5．以上述三种多胺为配体与六水合硝酸钻进行惰性气氛下的液－固
反应、在真空条件下的气－固反应、非水溶剂液相合成。本章依据以上
四章的结果，探讨了阴离于对氧载体氧合性能的影响。
6 提出了一个用活性纳米MnO。作氧化剂合成2，6一H甲酚基对
甲苯酚的新方法。
Oxygen carriers are certain important transition metal complexes which can transport and store dioxygen reversibly in living bodies. The study on oxygen carriers is of important significance in military and civil applications, especially in the fields of dioxygen separation, metal anti-corrosion and keeping Suits fresh.
Recently, solid-state reaction shows its great advantages in coordination chemistry. It breaks through rules of traditional liquid phase reaction and certain products can only be prepared by solid-state reactioa So introduction of solid-state reaction into the research of transition metal complexes of oxygen carriers would get a new break To establish this view, we have used solid-state reaction method to prepare some cobalt complexes as oxygen carriers, to study their oxygenation properties and to compare them with those obtained from classic liquid phase methods. The contents of this work contain six parts:
1. Recent development of oxygenation of cobalt complexes was reviewed, such as the structure and properties of some typical oxygen carriers. Their significance as model of natural oxygen carriers and potential applications in industrial processes were discussed..
2. A series of cobalt complexes were prepared from 1,3-diaminopropane , 1,4-diamino-butane, 3,3'-diaminodipropylamine with cobalt(II) chloride anhydrous, cobah(II) chloride hexahydrate via liquid-solid reaction , gas-solid reaction in room temperature and non-aqueous solution reactioa The influence of coordinated water to oxygenating properties of the complexes prepared by liquid-solid reaction was discussed.
3. A series of cobalt complexes were prepared from the three amines mentioned above and cobalt (II) sulfate anhydrous, cobalt (II) sulfate heptahydrate by the three
preparing ways above. The influence of coordinated water to oxygenating properties of the complexes prepared by liquid-solid reaction was discussed
4. Cobalt complexes were prepared from the three amines above and cobalt (II) acetate tetrahydrate by the three ways above. The result showed that complexes prepared by different amines have different oxygenating properties.
5. Cobalt complexes were prepared from the three amines above and cobak (II) nitrate hexahydrate by the three ways above. The influence of anion to the ability of oxygen carriers was discussed.
6. A new method of the preparation of 2,6-diformyl-4-methylphenol was presented Nanophase MnO2 was prepared and used in the synthesis of 2,6-diformyl-4-methylphenol.
引文
1. D. Fremy, Ann. Chim. Phys., 1852, 35: 271.
2. N. Farrel, D. H. Dolphin and D. T. Sawyer, J. Am. Chem. Soc., 1978, 100: 324.
3. L. Vaska, Acc. Chem. Res., 1976, 9: 175.
4. C. J. Weschler, B. M. Hoffman and F. Basolo, J. Am. Chem. Soc., 1975,97:5278
5. S. K. Cheung, C. J. Grimes and J. Wong, J. Am. Chem. Soc., 1976, 98: 5028.
6. L. J. Willson, M. G. Simmons, J. C. S. Comm., 1977, 634.
7. A. Werner, A. Mylius, Z. anory, Allg. chem., 1898,16:245
8. A. Werner, Ann. Chem., 1910, 375:1.
9. L. Pauling, C. D. Corywell, Proc. Natl. Acad. Sci., USA., 1936, 22: 210.
10. T. Tsumaki, Bull. Chem. Soc. Jpn., 1938, 13: 252.
11. M. Calvin, R. H. Bailes and W. K. Wilmarth, J. Am. Chem. Soc., 1946, 68: 2254.
12. C. H. Barkelew and M. Calvin, J. Am. Chem. Soc., 1946, 68: 2257.
13. W. K. Wilmarth, S. Aranoff and M. Calvin, J. Am. Chem. Soc., 1946, 68: 2263.
14 M. Calvin and C. H. Barkelew, J. Am. Chem. Soc., 1946, 68: 2267.
15. E. W. Hughes, W. K. Wilmarth and M. Calvin, J. Am. Chem. Soc., 1946, 68: 2273.
16. R. H. Ball, G. D. Dorough and M. Calvin, J. Am. Chem. Soc., 1946, 68: 2278.
17. P. Burk, J. Hearon, A. Schade, J. Biol. Chem., 1946, 165: 723.
18. J. Hearon, H. Leavy, A. Schade, et al, Fed. Proc. Fed. Am. Soc. Exp. Biol., 1947, 7: 713.
19. W. M. Latimer, The Oxidation State of the Elements and their Potential in Aqueous Solution, Prenttice Hall, New York, 1952: 38.
20. J. H. Wang, J. Am. Chem. Soc., 1958, 80: 3168.
21. F. Miller, J. Simplicio, R. G. Wilkins, J. Am. Chem. Soc., 1969, 91: 1962.
22. R. Nakon, A. E. Martell, J. Inorg. Chem., 1972, 34: 1365.
23. F. Miller, R. G. Wilkins, J. Am. Chem. Soc., 1970, 92: 2687.
24. U. Thewalt, R. E. Marsh, Inorg. Chem., 1972, 11: 35.
25. G. Mclendon, A. E. Martell, J. C. S. Chem. Comm., 1975, 223.
26. R. H. Michael, A. G. Sykes, J. C. S. Dalton., 1974, 1550.
27. C. Floriani, E. Calderazzo, J. Chem. Soc. (A), 1969, 946.
28. E. Alderazzo, C. Floriani and J. J. Salzman, Inorg. Nucl. Chem. Lett., 1966, 2: 379.
29. A. L. Crumbliss, F. Basolo, Science, 1969, 164: 1168.
30. A. L. Crumbliss, F. Basolo, J. Am. Chem. Soc., 1970, 92: 55.
31. V. L. Goedken, N. K. Kildahl and D. H. Busch, J. Coord. Chem., 1977, 7: 89.
32. L. S. Chen, M. E. Koehlrrer and B. C. Pestel et al, J. Am. Chem. Soc., 1978, 100: 7423.
33. G. Mclendon, M. Mason, Inorg. Chem., 1978, 17: 362.
34．戴寰，李进，韩志坚等，无机化学，1988，4(1)：61．
35．韩志坚，周洪，陈汉文等，无机化学学报，1992，8，421．
36. Jide Wang, Bull. Soc. Thim. Fr., 1994,131:30-36
37．王吉德，王瑶，张翼等，应用化学，1998，15(2)：97-99
38．张翼，王吉德，岳凡，电化学，2000，6(1)：45-50
39．岳凡，王吉德，崔勇，化学研究与应用，2000，12(6)：664
40．曹艳霞，岳凡，王吉德，迟姚玲，物理化学学报，2002，18(4)：364-367
41. C. K. Chang, T. G. Taylor, J. Am. Chem. Soc., 1973, 95:8475
42. E. C. Niederhoffer, J. H. Timmons, A. E. Martell, Chem. Rev., 1984, 84: 137.
43. D. H. Busch and N. W. Alcock, Chem. Rev., 1994, 94: 584.
44. B. Michael, S. Siegfried, D. K. Kenneth, et al., Inorg. Chem.,1999, 3 1989.
45. V. B. Paul, A. J. Lathe, Inorg. Chem., 1999, 38: 5086.
46．钟超凡，邓建成，童钰等，高等学校化学学报，1998，19(2)，174．
47. N. Hoshino, A. Jircitano, D. H. Busch, Inorg. Chem., 1988, 27: 2292.
48．李晓燕，孙宏建，孙东方，化学学报，1995，53：336．
49．鄢家明，谢如刚，赵华明，化学学报，1996，54：304．
50. A. Llobet, A. E. martell, M. A. Martinez, J. Mol. Catal. A:Chem., 1998,129(1):19
51. Shinoura Misato, Kita Satoru, Ohba Masaaki, et al., Japan. Inorg. Chem., 2000, 39: 4520.
52. Furutachi Hideki, Fujinami Shuhei, Suzuki et al., Japan. Dalton., 2000, 16: 2761
53. E. Martell, R. J. Motekaitis, D. Chen, et al., Supramol. Chem., 1996, 6: 333.
54. V. R. Elena, William Otto, D. Peter et al., Inorg. Chem,, 1997, 36: 2746.
55．贾永会，孔德领，俞耀庭等，功能高分子学报，1998，11：379．
56．岳凡，王吉德，唐军等，中国化学会全国第五界无机化学学术会议论文集，2000．
57．曹艳霞，王吉德，岳凡等，化学通报，2001，12：789．
58. Eishun Tsuchida, Kenichi Oyaizu, Eniya Listiani Dewi et al., Inorg. Chem., 1999, 38: 3704.
59．古凤才，王金明，刘荫藩等，天津大学学报，1998，31：666．
60．贾密英，王静秋，河北师范大学学报(自然科学版)，1997，21：295．
61．计亮年，第七届全国大环化合物学术讨论会，1994．
62. K. Kasuga, Y. Iida, Y. Yamaoto, Inorg. Chim. Acta, 1984, 84: 113.
63. I. A. Coher, W. S. Caughey, Biochem., 1968, 17: 636.
64. G. S. Hammond, C. Wu, S. Chem. Set., 1968,77:186
65. M. Momenteau, D. Lavaletta, J. Chem. Soc., Chem. Commun., 1982, 104: 341.
66. P. K. Sharma, A. K. Sen, S. N. Dubeg, Indian J. Chem. (A), 1944, 33: 1031.
67．吴惠康，杨维达，化学学报，1986，44(9)：1000．
68. Alcock N. W., Moore P, Omar H. A. A., J. Chem. Soc., Dalton Trans., 1986, 1: 985.
69. Alcock N. W., Moore P., Pierpoint C., J. Chem. Soc., Dalton Trans., 1984, 6: 2371.
70. Alcock N. W., Moore P., Omar H. A. A., J. Chem. Soc., Commun., 1985, 6: 1058.
71. Balakrishnan K. P., Omar H. A. A., Moore E, et al., J. Chem. Soc., Dalton Trans., 1990, 7: 2965.
72．王荣民，王云普，高分子通报，1998，1：33．
73. Adams H., Bailey N. A., Bertrand P., et al., J. Chem. Soc., Dalton Trans., 1996, 8: 1181.
74. E. Fujita, C. Creutz, N. Sutjn et al., J. Am. Chem. Soc., 1991, 113: 343.
75. P. M. Hrrison, Metalloproteins, London. Macmillan Press Led.
76．郑志风，徐宏，董岩等，化学世界，2001，8：435．
77. V. B. paul, A. J. Lathe, Inorg. Chem., 1999,38,5086
78．张宝峰，穆斯堡尔谱学，天津：天津大学出版社，1991，2504．
79．计亮年，第七届全国大环化合物学术讨论会，1994
80. L. N. Ji, M. Liu, J. Mol. Catal, 1991,70,247
81．杨继萍，朱鹤孙，黄鹏程，高分子材料科学与工程，1998，14(6)：41
82．何勇，杨继萍，黄鹏程等，功能高分子学报，1997，10，384
83．W．R．Anthony著，苏勉曾，谢高阳，申泮文等译，固体化学及其应用，复旦大学出版社，1989，7
84．周益明，忻新泉，无机化学学报，1999，15，274
85．赖芝，忻新泉，周衡南，无机化学学报，1997，13，330
86. X.Q.Xin,L.M.Zheng,J.Solid.State.Chem., 1993,106,451
87. X.B.Yao,L.M.Zheng,X.Q.Xin, J.Solid.State. Chem., 1995,117,333
88. L.X.Lei,X.Q.Xin,J.Solid.State.Chem.,1995,119,299
89. J.P.Lang,X.Q.Xin,J.Solid.State.Chem.,1994,108,118
90．贾殿增，杨立新，夏熙，化学学报，1998，56，154
91．余建群，贾殿增，张慧等，化学通报，1998，2，35
92．贾殿增，余建群，夏熙，科学通报，1998，43(2)，172
93．余建群，贾殿增，郑毓峰等，无机化学学报，1999，15，95
94．金斗满，朱文祥编著，配位化学研究方法，科学出版社，北京，1996
95．中本一雄著，黄德如，汪庆仁译，无机和配位化合物的红外和拉曼光谱，化学工业出版社，北京，1986
96．徐如人，庞文琴主编，无机合成与制备化学，高等教育出版社，北京，2001
97. (a)N. Strater, T. Klabunde, P. Tucker, et al. Science, 1995, 268:1489; (b)C.R. Kinssinger, H.E. Parge, D.R. Kghiton, et al. Nature, 1995, 678:641; (c) J.A. Sigman, C.K. Brian, A. Gengenbach, et al. J. Am. Chem. Soc., 2000, 122:8192; (d)吴建中，无机化学学报，2000, 16 (5): 697。
98. (a)J.D. Wang, A.E. Martell, R.J. Motekaitis, et al. Inorg. Chim. Acta., 2001,324:194; (b)H. Okawa, H. Furutachi, D.E. Fenton. Coord. Chem. Rev., 1998,174:51
99. F. Ullmann and K. Britiner, Chem. Ber., 1909, 42:2539
100．赵丽丽，王榕树，牛文泰等，物理化学学报，2002，18(3)：197
101．谢亚勃，马子川，郑世钧，河北师范大学学报，2001，25(1)：96
2. N. Farrel, D. H. Dolphin and D. T. Sawyer, J. Am. Chem. Soc., 1978, 100: 324.
3. L. Vaska, Acc. Chem. Res., 1976, 9: 175.
4. C. J. Weschler, B. M. Hoffman and F. Basolo, J. Am. Chem. Soc., 1975,97:5278
5. S. K. Cheung, C. J. Grimes and J. Wong, J. Am. Chem. Soc., 1976, 98: 5028.
6. L. J. Willson, M. G. Simmons, J. C. S. Comm., 1977, 634.
7. A. Werner, A. Mylius, Z. anory, Allg. chem., 1898,16:245
8. A. Werner, Ann. Chem., 1910, 375:1.
9. L. Pauling, C. D. Corywell, Proc. Natl. Acad. Sci., USA., 1936, 22: 210.
10. T. Tsumaki, Bull. Chem. Soc. Jpn., 1938, 13: 252.
11. M. Calvin, R. H. Bailes and W. K. Wilmarth, J. Am. Chem. Soc., 1946, 68: 2254.
12. C. H. Barkelew and M. Calvin, J. Am. Chem. Soc., 1946, 68: 2257.
13. W. K. Wilmarth, S. Aranoff and M. Calvin, J. Am. Chem. Soc., 1946, 68: 2263.
14 M. Calvin and C. H. Barkelew, J. Am. Chem. Soc., 1946, 68: 2267.
15. E. W. Hughes, W. K. Wilmarth and M. Calvin, J. Am. Chem. Soc., 1946, 68: 2273.
16. R. H. Ball, G. D. Dorough and M. Calvin, J. Am. Chem. Soc., 1946, 68: 2278.
17. P. Burk, J. Hearon, A. Schade, J. Biol. Chem., 1946, 165: 723.
18. J. Hearon, H. Leavy, A. Schade, et al, Fed. Proc. Fed. Am. Soc. Exp. Biol., 1947, 7: 713.
19. W. M. Latimer, The Oxidation State of the Elements and their Potential in Aqueous Solution, Prenttice Hall, New York, 1952: 38.
20. J. H. Wang, J. Am. Chem. Soc., 1958, 80: 3168.
21. F. Miller, J. Simplicio, R. G. Wilkins, J. Am. Chem. Soc., 1969, 91: 1962.
22. R. Nakon, A. E. Martell, J. Inorg. Chem., 1972, 34: 1365.
23. F. Miller, R. G. Wilkins, J. Am. Chem. Soc., 1970, 92: 2687.
24. U. Thewalt, R. E. Marsh, Inorg. Chem., 1972, 11: 35.
25. G. Mclendon, A. E. Martell, J. C. S. Chem. Comm., 1975, 223.
26. R. H. Michael, A. G. Sykes, J. C. S. Dalton., 1974, 1550.
27. C. Floriani, E. Calderazzo, J. Chem. Soc. (A), 1969, 946.
28. E. Alderazzo, C. Floriani and J. J. Salzman, Inorg. Nucl. Chem. Lett., 1966, 2: 379.
29. A. L. Crumbliss, F. Basolo, Science, 1969, 164: 1168.
30. A. L. Crumbliss, F. Basolo, J. Am. Chem. Soc., 1970, 92: 55.
31. V. L. Goedken, N. K. Kildahl and D. H. Busch, J. Coord. Chem., 1977, 7: 89.
32. L. S. Chen, M. E. Koehlrrer and B. C. Pestel et al, J. Am. Chem. Soc., 1978, 100: 7423.
33. G. Mclendon, M. Mason, Inorg. Chem., 1978, 17: 362.
34．戴寰，李进，韩志坚等，无机化学，1988，4(1)：61．
35．韩志坚，周洪，陈汉文等，无机化学学报，1992，8，421．
36. Jide Wang, Bull. Soc. Thim. Fr., 1994,131:30-36
37．王吉德，王瑶，张翼等，应用化学，1998，15(2)：97-99
38．张翼，王吉德，岳凡，电化学，2000，6(1)：45-50
39．岳凡，王吉德，崔勇，化学研究与应用，2000，12(6)：664
40．曹艳霞，岳凡，王吉德，迟姚玲，物理化学学报，2002，18(4)：364-367
41. C. K. Chang, T. G. Taylor, J. Am. Chem. Soc., 1973, 95:8475
42. E. C. Niederhoffer, J. H. Timmons, A. E. Martell, Chem. Rev., 1984, 84: 137.
43. D. H. Busch and N. W. Alcock, Chem. Rev., 1994, 94: 584.
44. B. Michael, S. Siegfried, D. K. Kenneth, et al., Inorg. Chem.,1999, 3 1989.
45. V. B. Paul, A. J. Lathe, Inorg. Chem., 1999, 38: 5086.
46．钟超凡，邓建成，童钰等，高等学校化学学报，1998，19(2)，174．
47. N. Hoshino, A. Jircitano, D. H. Busch, Inorg. Chem., 1988, 27: 2292.
48．李晓燕，孙宏建，孙东方，化学学报，1995，53：336．
49．鄢家明，谢如刚，赵华明，化学学报，1996，54：304．
50. A. Llobet, A. E. martell, M. A. Martinez, J. Mol. Catal. A:Chem., 1998,129(1):19
51. Shinoura Misato, Kita Satoru, Ohba Masaaki, et al., Japan. Inorg. Chem., 2000, 39: 4520.
52. Furutachi Hideki, Fujinami Shuhei, Suzuki et al., Japan. Dalton., 2000, 16: 2761
53. E. Martell, R. J. Motekaitis, D. Chen, et al., Supramol. Chem., 1996, 6: 333.
54. V. R. Elena, William Otto, D. Peter et al., Inorg. Chem,, 1997, 36: 2746.
55．贾永会，孔德领，俞耀庭等，功能高分子学报，1998，11：379．
56．岳凡，王吉德，唐军等，中国化学会全国第五界无机化学学术会议论文集，2000．
57．曹艳霞，王吉德，岳凡等，化学通报，2001，12：789．
58. Eishun Tsuchida, Kenichi Oyaizu, Eniya Listiani Dewi et al., Inorg. Chem., 1999, 38: 3704.
59．古凤才，王金明，刘荫藩等，天津大学学报，1998，31：666．
60．贾密英，王静秋，河北师范大学学报(自然科学版)，1997，21：295．
61．计亮年，第七届全国大环化合物学术讨论会，1994．
62. K. Kasuga, Y. Iida, Y. Yamaoto, Inorg. Chim. Acta, 1984, 84: 113.
63. I. A. Coher, W. S. Caughey, Biochem., 1968, 17: 636.
64. G. S. Hammond, C. Wu, S. Chem. Set., 1968,77:186
65. M. Momenteau, D. Lavaletta, J. Chem. Soc., Chem. Commun., 1982, 104: 341.
66. P. K. Sharma, A. K. Sen, S. N. Dubeg, Indian J. Chem. (A), 1944, 33: 1031.
67．吴惠康，杨维达，化学学报，1986，44(9)：1000．
68. Alcock N. W., Moore P, Omar H. A. A., J. Chem. Soc., Dalton Trans., 1986, 1: 985.
69. Alcock N. W., Moore P., Pierpoint C., J. Chem. Soc., Dalton Trans., 1984, 6: 2371.
70. Alcock N. W., Moore P., Omar H. A. A., J. Chem. Soc., Commun., 1985, 6: 1058.
71. Balakrishnan K. P., Omar H. A. A., Moore E, et al., J. Chem. Soc., Dalton Trans., 1990, 7: 2965.
72．王荣民，王云普，高分子通报，1998，1：33．
73. Adams H., Bailey N. A., Bertrand P., et al., J. Chem. Soc., Dalton Trans., 1996, 8: 1181.
74. E. Fujita, C. Creutz, N. Sutjn et al., J. Am. Chem. Soc., 1991, 113: 343.
75. P. M. Hrrison, Metalloproteins, London. Macmillan Press Led.
76．郑志风，徐宏，董岩等，化学世界，2001，8：435．
77. V. B. paul, A. J. Lathe, Inorg. Chem., 1999,38,5086
78．张宝峰，穆斯堡尔谱学，天津：天津大学出版社，1991，2504．
79．计亮年，第七届全国大环化合物学术讨论会，1994
80. L. N. Ji, M. Liu, J. Mol. Catal, 1991,70,247
81．杨继萍，朱鹤孙，黄鹏程，高分子材料科学与工程，1998，14(6)：41
82．何勇，杨继萍，黄鹏程等，功能高分子学报，1997，10，384
83．W．R．Anthony著，苏勉曾，谢高阳，申泮文等译，固体化学及其应用，复旦大学出版社，1989，7
84．周益明，忻新泉，无机化学学报，1999，15，274
85．赖芝，忻新泉，周衡南，无机化学学报，1997，13，330
86. X.Q.Xin,L.M.Zheng,J.Solid.State.Chem., 1993,106,451
87. X.B.Yao,L.M.Zheng,X.Q.Xin, J.Solid.State. Chem., 1995,117,333
88. L.X.Lei,X.Q.Xin,J.Solid.State.Chem.,1995,119,299
89. J.P.Lang,X.Q.Xin,J.Solid.State.Chem.,1994,108,118
90．贾殿增，杨立新，夏熙，化学学报，1998，56，154
91．余建群，贾殿增，张慧等，化学通报，1998，2，35
92．贾殿增，余建群，夏熙，科学通报，1998，43(2)，172
93．余建群，贾殿增，郑毓峰等，无机化学学报，1999，15，95
94．金斗满，朱文祥编著，配位化学研究方法，科学出版社，北京，1996
95．中本一雄著，黄德如，汪庆仁译，无机和配位化合物的红外和拉曼光谱，化学工业出版社，北京，1986
96．徐如人，庞文琴主编，无机合成与制备化学，高等教育出版社，北京，2001
97. (a)N. Strater, T. Klabunde, P. Tucker, et al. Science, 1995, 268:1489; (b)C.R. Kinssinger, H.E. Parge, D.R. Kghiton, et al. Nature, 1995, 678:641; (c) J.A. Sigman, C.K. Brian, A. Gengenbach, et al. J. Am. Chem. Soc., 2000, 122:8192; (d)吴建中，无机化学学报，2000, 16 (5): 697。
98. (a)J.D. Wang, A.E. Martell, R.J. Motekaitis, et al. Inorg. Chim. Acta., 2001,324:194; (b)H. Okawa, H. Furutachi, D.E. Fenton. Coord. Chem. Rev., 1998,174:51
99. F. Ullmann and K. Britiner, Chem. Ber., 1909, 42:2539
100．赵丽丽，王榕树，牛文泰等，物理化学学报，2002，18(3)：197
101．谢亚勃，马子川，郑世钧，河北师范大学学报，2001，25(1)：96