在THF溶劑中以1:1的比例混合Ni(ClO4)2．6H2O與P(o-C6H4SH)3 可形成雙核化合物Ni2{P(o-C6H4S)2(o-C6H4SH)}2 (1)。化合物1由兩個扭曲的平面四方形N(II)組成，每一個Ni(II)配位三個thiolate與一個phosphorus，其中兩個thiolate將兩個Ni(II)橋接起來。化合物1具有兩個未鍵結到Ni(II)的S-H，經由IR (νS-H 2391cm-1), 1H NMR (δ 5.88(s))和X-ray單晶繞射結構，證實化合物1中具有[Ni-S…H-S] 以及[Ni…H-S]兩種分子內的作用。X-ray單晶繞射結構的研究推測化合物1傾向以[Ni…H-S]形式的交互作用穩定未配位到Ni(II)的S-H。
　以1:2的比例混合Ni(ClO4)2．6H2O與P(o-C6H4SH)3於THF中，可以得到單核化合物Ni{P(o-C6H4S)(o-C6H4SH)2}2 (3)。化合物3配位了兩個phosphorus 與兩個thiolate，形成平面四方型的結構，另外還具有4個未配位到Ni(II)的Ｓ-H。由X-ray單晶繞射結構推測化合物3具有輕微[Ni-S…H-S]或[Ni…H-S]兩種分子內的交互作用。化合物1與3加入過量的Lewis base Et3N ，可得到已知的雙核化合物[Et3NH]2[Ni2{P(o-C6H4S)3}2] (2)。
　利用[PPN][Fe(CO)4(CN)]和bis(2-aminophenyl) disulfide反應得到六配位化合物[PPN][Fe(CO)2(CN)(S,NH2-C6H4)(S-C6H4NH2)] (5)。將化合物3通入氧氣，或加入等當量的Lewis baseＥt3N 可得到穩定之五配位化合物[PPN]　[Fe(CO)2(CN)(S,NH-C6H4)] (6)。合成並分離出化合物5，證實合成價電子數為16的5配位化合物6的反應步驟，[PPN][Fe(CO)4(CN)]先經過經由oxidative addition，CO ligand dissociation形成化合物5，base與化合物5的chelating ligand [S,NH2-C6H4]- amine proton發生deprotonation，使得chelating ligand [S,NH-C6H4]- 供給電子能力增加，terminal ligand [S,NH2-C6H4]-離開Fe(II)，得到化合物6。

Reaction of Ni(ClO4)2．6H2O with 1 equiv. of P(o-C6H4SH)3 in THF leads to the formation of a dimeric complex, Ni2{P(o-C6H4S)2(o-C6H4SH)}2 (1). Complex 1 contains distorted square planar, diamagnetic Ni(II) centers ligated by a phosphorus, a terminal thiolate, two thiolates that bridge to the second Ni, and a S-H proton directly interacting with both nickel and sulfur atoms. The presence of combination of intramolecular [Ni-S…H-S] /[Ni…H-S] interactions was verified in the solid state by the observation of IR νSH stretching band (2391cm-1), 1H NMR (δ5.880(s) in CDCl3) and subsequently confirmed by X-ray diffraction study. Isolation and characterization of complex 1 may reflect the existence of Ni-R/Ni-SIa atates as [(Scys-H)Ni(Scys)3Fe] corrdination environment in [NiFe] hydrogenase. Reaction of Ni(ClO4)2．6H2O with 2 equiv. of P(o-C6H4SH)3 in THF results in the formation of mononuclear and square planar complex, Ni{P(o-C6H4S)(o-C6H4SH)2}2 (3) with four S-H protons, where Nickel is coordinated by two sulfurs and two phosphorus. X-ray diffraction study indicate that two bulky ligands, {P(o-C6H4S)(o-C6H4SH)2}, keeps S-H proton away from nickel and sulfur atoms and there were weak intramolecular [Ni-S…H-S] /[Ni…H-S] interactions in complex 3. The thiol proton in complex 1 and 3 was easily removed by Lewis base Et3N to yield the known Ni(II) dimer [NiII(P(o-C6H4S)3)]22- (2).
The hexacoordinate Fe(II) complex [PPN][Fe(CO)2(CN)(S,NH2-C6H4)(S-C6H4NH2) (5) was prepared by the reaction of 2-aminophenyl disulfide and [PPN][Fe(CO)4(CN)]. Upon contact with dry O2, or treated with Lewis base Et3N, complex 5 turned to the pentacoordinate Fe(II) complex [PPN][Fe(CO)2(CN)(S,NH-C6H4)] (6).

1. Adams, M. W.; Stidfel, E. I. Science 1998, 282, 1842
2. Paschos, A.; Glass, R. S. ; Book, A. FEBS Letters 2000, 488, 9
3. Peck, H. D.; Pietro, A. San; Gest, H. Proc. Natl. Actad. Sci. 1956, 42, 13
4. Graf, E.G.; Thauer, R. K. FEBS Letters 1981, 136, 165
5. Darensbourg, M. Y.; Lyon, E. J.; Smee J. J. Coord. Chem. Rev. 2000, 206-207, 533
6. Nicolet, Y.; Piras, C.; Legrand, P.; Hatchikian, C. E.; Fontecilla-Camps, J. C. Structure 1999, 7, 12
7. Higuchi, Y.; Ogata, H.; Miki, K.; Yasuoka, N.; Yagi, T. Sturcture 1999, 7, 549
8. Peters, J. W.; Lanzilotta, W. N.; Lemon, B. J.; Seefeldt, L. C. Science 1998, 282, 1853
9. Volbed, A.; Gharon, M. H.; Piras, C.; Hatchikian, E. C.; Frey, M.; Fontecilla-Camps J. C. Nature 1995, 737, 580
10. Volbed, A.; Garcin, E.; Piras, C.; de Lacey, A. L.; Fernadez, V. M.; Hatchikian, E. C.; Frey, M.; Fontecilla-Camps J. C. J. Am. Chem. Soc. 1996, 96, 3031
11. Fontecilla-Camps, J. C. Structure. Bonding 1998, 91, 1
12. Marr, A. C.; Spencer, Douglas J.E.; Martin Schröder Coord. Chem. Rev. 2001, 219-221, 1055
13. Montat, Y.; Amara, P.; Volbeda, A.; Vernede, X.; Hatchikian, E. C.; Field, M. J.; Frey, M.; Fontcilla-Camps, J. C. Nature Sturct. L Biol. 1997, 119, 7181
14. Davies, S. C.; Evans, D. J.; Hughes, D. L.; Longhurst, S.; Sanders, J. R. J. Am. Chem. Commun. Soc. 2000, 122, 488
15. LeGall, J.; Ljungdahl, P. O.; Moura, I.; Peck, H. D.; Xavier, A. V.; Moura, J. J. G.; Teixerira, M.; Huynh, B. H.; Dervartanuan, D. V. Biochem. Biophy. Res. Commun, 1982, 34, 5527
16. Poberts, L. M.; Lindahl, P. A. Biochemistry, 1994, 33, 14339
17. Bagley, K. A.; Duin, E. C.; Roseboon, W.; Albracht, S. P. J.; Woodruff, W. H. Biochemistry, 1995, 34, 5527
18. de Lacey, A. L.; Hatchikian, C. E.; Volbeda, A.; Fontecilla-Camps, J. C. J. Am. Chem. Soc. 1997, 119, 7181
19. Ogata, H.; Mizoguchi, Y.; Mizuno, N.; Miki, K.; Adachi, S.-I.; Yasuoka, N.; Yagi, T.; Yamauchi, O.; Hirota, S.; Higuchi, Y. J. Am. Chem. Soc. 2002, 124, 11628
20. Siegbahn, P. E. M.; Blomberg, M. R. A.; Wirstam nee Pavlov, M. Crabtree, R. H. J. Bio. Inorg. Chem. 2001, 6, 460
21. Fan, H.-J.; Hall, M. B. J. Am. Chem. Soc. 2002, 124, 394
22. Davidson, G.; Choudhury, S. B.; Gu, Z.; Bose, K.; Roseboom, W.; Albracht, S. P. J.; Maroney, M. J. Bichemistry 2000, 5, 36
23. Barondeau, D. P.; Roberts, L. M.; Lindahl, P. A. J. Am Chem. Soc. 1994, 116, 3442
24. Albracht, S. P. J. Biochim, Biophys. Acta. 1994, 1188, 167
25. Roberts. L. M.; Lindahl, P. A. Biochemistry 1994, 33, 14339
26. Baidya, N.; Olmstead, M.; Mascharak, P. K. Inorg. Chem. 1991, 30, 929
27. Baidya, N.; Olmstead, M.;Whitehead, J. P.;Bagyinka, C.; Maroney, M. J.; Mascharak, P. K. Inorg. Chem. 1992, 31, 3612
28. Baidya, N.; Olmstead, M.; Mascharak, P. K. J. Am. Chem. Soc. 1993, 115, 4665
29. Volbeda, A.; Garain, E.; Piras, C.; Delacey, A. L.; Fernandez. V. M.; Hatchikian, E. C.; Frey, M.; Fontecilla-Camps J. C. J. Am. Chem. Soc. 1996, 118, 12989
30. Sellmann, D.; Geipel, F.; Moll, M. Angew. Chem. Int. Edt. Engl. 2000, 39, 561
31. Forester, S.; Stein, M.; Brecht, M.; Ogata, H.; Higuchi, Y.; Lubitz, W. J. Am. Chem. Soc. 2003, 125, 83
32. (a) Fan, C.; Teixeira, M.; Moura, J.; Moura, I.; Huynh, B. H.; Le Gall, J.; Peck, H. D., Jr; Hoffman, B. M. J. Am. Chem. Soc. 1991, 113, 20-24 (b) Whitehead, J. P.; Gurbiel, R. J.; Bagyinka, C.; Hoffman, B. M.; Maroney, M. J. J. Am. Chem. Soc. 1993, 115, 5629
33. Smith, M.C.; Longhurst, S.; Barclay, J. E.; Cramer, S. P.; Davies, S. C.; Hughes, D. L.; Gu. W.-W.; Evans, D. J. J. Chem. Soc., Dalton Trans., 2001, 1387
34. Sellmann, D.; Geipel, F.; Lauderbach, F.; Heinemann, F. W. Angew. Chem. Int. Ed. 2002, 41, 632
35. Davies, S. C.; Evans, D. J.; Hughes, D. L.; Longhurst, S.; Sanders, J. R. Chem. Commun. 1999, 1935
36. Lai, C.-H.; Reibenspies, J. H.; Darensbouorg, M. Y. Angew. Chem. Int. Ed. Engl. 1996, 35, 2390
37. Rauchfuss, T. B.; Roundhill, D. M. J. Am Chem. Soc 1975, 97, 3386
38. Bouwmann, E.; Henderson, R. K.; Spek, A. L.; Reedijk, J.; Eur, J. Inorg, Chem. 1999, 217
39. Block, E.; Ofori-Okai, G.; Zubieta, J. J. Am. Chem. Soc. 1989, 111, 2327
40. Liaw, W.-F.; Lee N.-H.; Chen, C.-H.; Lee, C.-M.; Lee, G.-H.; Peng, S.-M. J. Am. Chem. Soc. 2000, 122, 488
41. Davies, S. C.; Evans, D. J.; Hughes, D. L.; Longhurst, S. Acta. Cryst. 1999, C55, 1436
42. Franolic, J. D.; Wang, W. Y.; Millar, M. J. Am. Chem. Soc. 1992, 114, 6587
43. Cotton, F. A.; Matusz, M.; Poli, R.; Feng, X. J Am. Chem. Soc. 1988, 110, 1144
44. Choudhury, S. B.; Pressler, M. A.; Mirza, S. A.; Day, R. O.; Maroney, M. J. Inorg. Chem. 1994, 33, 4831
45. Casalot, L.; Rousset, M. TRENDS in Microbiology 2001, 9, 228
46 Adams, M. W. W.; Stiefel, E. I. Science 1998, 282, 1842
47 Stein, M.; Lubitz, W. Phys. Chem. Chem. Phys. 2001, 3, 2668
48 Evans, D. J.; Pickett, C. J. Chem. Soc. Rev. 2003, 32, 268