為了解金屬與烴基硫的配位化學，在本研究中將二價鈷金屬起始物與(PS3")3– {[P(C6H3-3-Me3Si-2-S)3]3–}，(PS3')3– {[P(C6H3-5-Me-2-S)3]3–}進行反應。與 (PS3")3– 反應可得雙核鈷三價化合物的三種異構物，δ–[Co2(PS3")2] (1),、λ–[Co2(PS3")2] (2) 與 [Co2(PS3")2] (3)。化合物1、2為一對鏡像異構物，在其結構中具有似蝴蝶狀（butterfly–like）的 [Co2(μ2–S)2] core。化合物3為化合物1、2的結構異構物，在其結構中具有似鑽石狀（diamond–like）的 [Co2(μ2–S)2] core。
二價鈷金屬起始物與 (PS3')3– 反應可獲得二個混合價數雙核鈷二、三價的化合物，λ–[Co2(PS3')2]– (4) 與δ–[Co2(PS3')2]– (5)。4與5為鏡像異構物，且於1、2有類似的結構。

In our effort to understand metal thiolate coordination chemistry, we have explored the reactions of cobalt(II) with trisbenzenethiolatophosphine ligands such as (PS3')3– and (PS3")3–, where (PS3')3– = [P(C6H3-5-Me-2-S)3]3– and (PS3")3– = [P(C6H3-3-Me3Si-2-S)3]3–. The reactions of cobalt(II) with PS3" ligand led to three isomers of dicobalt(III/III) complexes, δ–[Co2(PS3")2] (1), λ–[Co2(PS3")2] (2) and [Co2(PS3")2] (3). Compounds 1 and 2 are a pair of enantiomers and consist of [Co2(μ2–S)2] butterfly–like core. Compound 3 is a structural isomer of 1 and 2 and contains a [Co2(μ2–S)2] diamond core. The reactions of cobalt(II) with PS3' ligand result in two mixed–valence dicobalt(II/III) complexes, λ–[Co2(PS3')2]– (4) and δ–[Co2(PS3')2]– (5). They are a pair of enantiomers and have geometries similar to those of 1 and 2.

1. Aresta, M.; Rossi, M.; Sacco, A., Tetrahedral complexes of cobalt(I). Inorg. Chim. Acta. 1969, 3, 227-231.
2. Haumann, M.; Meijboom, R.; Mossb, J. R.; Roodt, A., Synthesis, crystal structure and hydroformylation activity of triphenylphosphite modified cobalt catalysts Dalton Trans. 2004, (11), 1679 - 1686.
3. Bernhardt, E.; Finze, M.; Willner, H.; Lehmann, C. W.; Aubke, F., Salts of the Cobalt Complexes [Co(CO)5]+ and [Co(CO)2(NO)2]+ and the Lewis Acid-Base Adduct [Co2(CO)7CO—B(CF3)3]. Chem. Eur. J. 2006, 12, (32), 8276-8283.
4. Friedle, S.; Partyka, D. V.; Bennett, M. V.; Holm, R. H., Synthesis of metal dithiolene complexes by Si-S bond cleavage of a bis(silanylsulfanyl)alkene. Inorg. Chim. Acta. 2006, 359, (5), 1427-1434.
5. Bennett, B.; Holz, R. C., EPR Studies on the Mono- and Dicobalt(II)-Substituted Forms of the Aminopeptidase from Aeromonas proteolytica. Insight into the Catalytic Mechanism of Dinuclear Hydrolases. J. Am. Chem. Soc. 1997, 119, (8), 1923-1933.
6. Bennett, B.; Holz, R. C., Inhibition of the Aminopeptidase from Aeromonas Proteolytica by L-Leucinephosphonic Acid, a Transition State Analogue of Peptide Hydrolysis. J. Am. Chem. Soc. 1998, 120, (46), 12139-12140.
7. Epperson, J. D.; Ming, L.-J., Cobalt(II) and copper(II) binding of Bacillus cereus trinuclear phospholipase C: a novel 1H NMR spectrum of a ‘Tri-Cu(II)’ center in protein. J. Inorg. Biochem. 2001, 87, 149-156.
8. Strand, K. R.; Karlsen, S.; Andersson, K. K., Cobalt Substitution of Mouse R2 Ribonucleotide Reductase as a Model for the Reactive Diferrous State. Spectroscopic and Structural Evidence for A Ferromagnetically Coupled Dinuclear Cobalt Cluster. J. Biol. Chem. 2002, 277, (37), 34229-34238.
9. Crawford, P. A.; Yang, K.-W.; Sharma, N.; Bennett, B.; Crowder, M. W., Spectroscopic Studies on Cobalt(II)-Substituted Metallo-β-lactamase ImiS from Aeromonas veronii bv. sobria. Biochemistry 2005, 44, (13), 5168-5176.
10. Davis, R.; Bienvenue, D.; Swierczek, S.; Gilner, D.; Rajagopal, L.; Bennett, B.; Holz, R., Kinetic and spectroscopic characterization of the E134A- and E134D-altered dapE -encoded N -succinyl-l ,l -diaminopimelic acid desuccinylase from Haemophilus influenzae. J. Biol. Inorg. Chem. 2006, 11, (2), 206-216.
11. Randaccio, L.; Geremia, S.; Wuerges, J., Crystallography of vitamin B12 proteins. J. Organomet. Chem. 2007, 692, (6), 1198-1215.
12. Nagasawa, T.; Takeuchi, K.; Yamada, H., Characterization of a new cobalt-containing nitrile hydratase purified from urea-induced cells of Rhodococcus rhodochrous J1. Eur. J. Biochem. 1991, 196, (3), 581-589.
13. Katayama, Y.; Narahara, Y.; Inoue, Y.; Amanon, F.; Kanagawa, T.; Kuraishi, H., A thiocyanate hydrolase of Thiobacillus thioparus. A novel enzyme catalyzing the formation of carbonyl sulfide from thiocyanate. J. Biol. Chem. 1992, 267, (13), 9170-9175.
14. Krebs, B.; Henkel, G., Transition-Metal Thiolates: From Molecular Fragments of Sulfidic Solids to Models for Active Centers in Biomolecules. Angew. Chem. Int. Ed. Engl. 1991, 30, (7), 769-788.
15. Rauchfuss, T. B., The Coordination Chemistry of Thiophenes. Prog. Inorg. Chem. 1991, 39, 259-329.
16. Pullen, A. E.; Olk, R. M., The coordination chemistry of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) and isologs. coord. chem. rev. 1999, 188, 211-262.
17. Gray, H. B.; Williams, R.; Bernal, I.; Billig, E., A Spin-Free Square Planar Cobaltous Complex. J. Am. Chem. Soc. 1962, 84, (18), 3596-3597.
18. Krespan, C. G.; McKusick, B. C.; Cairns, T. L., Dithietene and Bicyclooctatriene Ring Systems from Bis-(fluoroalkyl)-acetylenes. J. Am. Chem. Soc. 1960, 82, (6), 1515-1516.
19. Enemark, J. H.; Lipscomb, W. N., Molecular Structure of the Dimer of Bis(cis-1,2-bis(trifluoromethyl)ethylene-1,2-dithiolate)cobalt. Inorg. Chem. 1965, 4, (12), 1729-1734.
20. Baker-Hawkes, M. J.; Dori, Z.; Eisenberg, R.; Gray, H. B., The crystal and molecular structure of the tetra-n-butylammonium salt of the dianionic dimer of bis(1,2,3,4-tetrachlorobenzene-5,6-dithiolato)cobaltate. J. Am. Chem. Soc. 1968, 90, (16), 4253-4259.
21. Kang, B.; Peng, J.; Hong, M.; Wu, D.; Chen, X.; Weng, L.; Lei, X.; Liu, H., Syntheses, structures and properties of tri-n-butylphosphine cobalt complexes containing o-benzenedithiolate ligands in unusual co-ordination modes. J. Chem. Soc., Dalton Trans. 1991, (11), 2897.
22. Carpenter, G. B.; Clark, G. S.; Rieger, A. L.; Rieger, P. H.; Sweigart, D. A., Dithiolenes revisited: an electron spin resonance study of some five-co-ordinate cobalt complexes and the crystal structures of [Co{S2C2(CF3)2}2{P(OPh)3] and [Co{S2C2(CF3)}2(PPh3)]. J. Chem. Soc., Dalton Trans. 1994, (20), 2903 - 2910.
23. Schrauzer, G. N.; Mayweg, V. P.; Finck, H. W.; Heinrich, W., Coordination Compounds with Delocalized Ground States. Bisdithiodiketone Complexes of Iron and Cobalt. J. Am. Chem. Soc. 1966, 88, (20), 4604-4609.
24. Balch, A. L., Cleavage reactions of cobalt and iron dithiolate compounds. Five-coordinate complexes. Inorg. Chem. 1967, 6, (12), 2158-2162.
25. Nochomovitz, Y. D.; Rieger, A. L.; Rieger, P. H.; Roper, B. J., Electron spin resonance study of the frozen-solution equilibrium [Co{S2C2(CF3)2}2L]+ L ↔ [Co{S2C2(CF3)2}2L2][L = P(OR)3 or PPh(OMe)2; R = alkyl]. J. Chem. Soc., Dalton Trans. 1996, (17), 3503 - 3506.
26. Swenson, D.; Baenziger, N. C.; Coucouvanis, D., Tetrahedral mercaptide complexes. Crystal and molecular structures of [(C6H5)4P]2M(SC6H5)4 complexes (M = cadmium(II), zinc(II), nickel(II), cobalt(II), and manganese(II)). J. Am. Chem. Soc. 1978, 100, (6), 1932-1934.
27. Dance, I. G., Synthesis, crystal structure, and properties of the hexa(.mu.-benzenethiolato)tetra(benzenethiolatocobaltate(II)) dianion, the prototype cobalt(II)-thiolate molecular cluster. J. Am. Chem. Soc. 1979, 101, (21), 6264-6273.
28. Koch, S. A.; Fikar, R.; Millar, M.; O'Sullivan, T., Steric control of metal-thiolate coordination: synthesis and structure of monomeric cobalt(II) and copper(I) thiolate complexes. Inorg. Chem. 1984, 23, (2), 121-122.
29. Corwin, D. T.; Fikar, R.; Koch, S. A., Four- and five-coordinate cobalt(II) thiolate complexes: models for the catalytic site of alcohol dehydrogenase. Inorg. Chem. 1987, 26, (19), 3079-3080.
30. Coucouvanis, D.; Murphy, C. N.; Kanodia, S. K., Metal-mercaptide chemistry. The synthesis and structural characterization of the [Cu(SC6H5)3]2- anion. A rational synthesis and the structure of the [Cu4(SC6H5)6]2- cluster. Inorg. Chem. 1980, 19, (10), 2993-2998.
31. Dance, I. G., The zinc-benzenethiolate-halide system. Synthesis and structure of the hexakis(.mu.-(benzenethiolato))-bis(benzenethiolato)dichlorotetrazincate(II) dianion. Inorg. Chem. 1981, 20, (7), 2155-2160.
32. Dance, I. G., Crystallization and structure of bis(tetramethylammonium) octakis(benzenethiolato)hexaargentate(I), extending the series of cages [M4(SPh)6]2-, [M5(SPh)7]2-, [M6(SPh)8]2-, and [M12(SPh)16]4-. Inorg. Chem. 1981, 20, (5), 1487-1492.
33. Hagen, K. S.; Stephan, D. W.; Holm, R. H., Metal ion exchange reactions in cage molecules: the systems [M4-nM'n(SC6H5)10]2- (M, M' = Fe(II), Co(II), Zn(II), Cd(II)) with adamantane-like stereochemistry and the structure of [Fe4(SC6H5)10]2-. Inorg. Chem. 1982, 21, (11), 3928-3936.
34. Davies, S. C.; Durrant, M. C.; Hughes, D. L.; Richards, R. L.; Sanders, J. R., Iron, cobalt and vanadium complexes of the N(CH2CH2S)33- ligand with chloride, azide, cyanide and carbonyl co-ligands. J. Chem. Soc., Dalton Trans. 2000, (24), 4694-4701.
35. Duran, N. r.; Clegg, W.; Cucurull-Sa´nchez, L.; Coxall, R. A.; Jime´nez, H. R.; Moratal, J.-M. a.; Lloret, F.; Gonza´lez-Duarte, P., Unprecedented Stabilization of Cobalt(II) in a Tetrahedral S2O2 Environment: The Use of a Redox-Noninnocent Ligand. Inorg. Chem. 2000, 39, (21), 4821-4832.
36. Kimblin, C.; Bridgewater, B. M.; Churchill, D. G.; Tony Hascall; Parkin, G., Bis(mercaptoimidazolyl)(pyrazolyl)hydroborato Complexes of Zinc, Cadmium, and Cobalt: Structural Evidence for the Enhanced Tendency of Zinc in Biological Systems to Adopt Tetrahedral M[S4] Coordination. Inorg. Chem. 2000, 39, (19), 4240-4243.
37. Noveron, J. C.; Olmstead, M. M.; Mascharak, P. K., Co(III) Complexes with Carboxamido N and Thiolato S Donor Centers: Models for the Active Site of Co-Containing Nitrile Hydratases. J. Am. Chem. Soc. 1999, 121, (14), 3553-3554.
38. Block, E.; Ofori-Okai, G.; Zubieta, J., 2-Phosphino- and 2-phosphinylbenzenethiols: new ligand types. J. Am. Chem. Soc. 1989, 111, (6), 2327-2329.
39. Janiak, C., A critical account on π-π stacking in metal complexes with aromatic nitrogen-containing ligands. J. Chem. Soc., Dalton Trans. 2000, (21), 3885-3896.
40. Jorgensen, W. L.; Severance, D. L., Aromatic-aromatic interactions: free energy profiles for the benzene dimer in water, chloroform, and liquid benzene. J. Am. Chem. Soc. 1990, 112, (12), 4768-4774.
41. Tsuzuki, S.; Honda, K.; Uchimaru, T.; Mikami, M.; Tanabe, K., Origin of Attraction and Directionality of the π/π Interaction: Model Chemistry Calculations of Benzene Dimer Interaction. J. Am. Chem. Soc. 2002, 124, (1), 104-112.
42. Ray, K.; Begum, A.; Weyhermüller, T.; Piligkos, S.; Slageren, J. v.; Neese, F.; Wieghardt, K., The Electronic Structure of the Isoelectronic, Square-Planar Complexes [FeII(L)2]2- and [CoIII(LBu)2]- (L2- and (LBu)2- = Benzene-1,2-dithiolates): An Experimental and Density Functional Theoretical Study. J. Am. Chem. Soc. 2005, 127, (12), 4403-4415.
43. He, L. P.; Yao, C. L.; Naris, M.; Lee, J. C.; Korp, J. D.; Bear, J. L., Molecular structure and chemical and electrochemical reactivity of tetrakis(N,N'-diphenylbenzamidinato)dicobalt and -dirhodium. Inorg. Chem. 1992, 31, (4), 620-625.
44. Clerac, R.; Cotton, F. A.; Daniels, L. M.; Dunbar, K. R.; Kirschbaum, K.; Murillo, C. A.; Pinkerton, A. A.; Schultz, A. J.; Wang, X., Linear Tricobalt Compounds with Di(2-pyridyl)amide (dpa) Ligands: Temperature Dependence of the Structural and Magnetic Properties of Symmetrical and Unsymmetrical Forms of Co3(dpa)4Cl2 in the Solid State. J. Am. Chem. Soc. 2000, 122, (26), 6226-6236.
45. Cle´rac, R.; Cotton, F. A.; Daniels, L. M.; Dunbar, K. R.; Murillo, C. A.; Wang, X., Tuning the Metal-Metal Bonds in the Linear Tricobalt Compound Co3(dpa)4Cl2: Bond-Stretch and Spin-State Isomers. Inorg. Chem. 2001, 40, (6), 1256-1264.
46. Nomura, M.; Fourmigué, M., Dinuclear Cp* Cobalt Complexes of the 1,2,4,5-Benzenetetrathiolate Bischelating Ligand. Inorg. Chem. 2008, 47, (4), 1301-1312.
47. Conradie, J.; Quarless, D. A.; Hsu, H. F.; Harrop, T. C.; Lippard, S. J.; Koch, S. A.; Ghosh, A., Electronic Structure and FeNO Conformation of Nonheme Iron-Thiolate-NO Complexes: An Experimental and DFT Study. J. Am. Chem. Soc. 2007, 129, (34), 10446-10456.
48. Yano, T.; Syuhei, H. A.; Yasuhiro, Y.; Koichiro, F.; Tomohiro, J.; Masuda, O. H., CoIII Complexes with Square-Planar N2S2- and N2(SO2)2-Type Ligands as An Active Site Structural Model for Nitrile Hydratase - Biological Implications of an Amidate Coordination. Eur. J. Inorg. Chem. 2006, 2006, (18), 3753-3761.