Synthesis and Characterization of Square Planar Nickel(II)-Arylthiolate Complexes with the Biphenyl-2,2'-dithiolate Ligand
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- 作者：Edurne Erkizia and Rebecca R. Conry
- 刊名：Inorganic Chemistry
- 出版年：2000
- 出版时间：April 17, 2000
- 年：2000
- 卷：39
- 期：8
- 页码：1674 - 1679
- 全文大小：102K
- 年卷期：v.39,no.8(April 17, 2000)
- ISSN：1520-510X
文摘
Two new NiIIS4 complexes with the biphenyl-2,2'-dithiolate ligand (L) are reported. The dinuclear complex 1,[Ni2L3]2-, was formed in the reaction of 2-3 equiv of Na2L and [NiCl4]2- and the mononuclear complex [NiL2]2-(2) by using 4-10 equiv of Na2L. Complexes 1 and 2 have been crystallographically characterized. (Et4N)2[1]·0.5S2Ph2, CH3CN: C60H71N3Ni2S7, triclinic, P
, a = 13.806(2) Å, b = 14.267(2) Å, c = 16.873(2) Å, 
=69.263(10)
, 
= 69.267(8), 
= 83.117(10), Z = 2, R1 = 0.0752 (wR2 = 0.2011). (Et4N)(Na·CH3CN)[2]:C34H39N2NaNiS4, triclinic, P, a = 9.9570(10) Å, b = 13.2670(10) Å, c = 13.9560(10) Å, = 108.489(7), = 90.396(6), = 103.570(4), Z = 2, R1 = 0.0390 (wR2 = 0.0995). Both complexes are square planar aboutthe nickel ion in the solid state as well as in solution. Most Ni(II)-thiolate complexes are square planar exceptthe tetrahedral mononuclear complexes with monodentate arylthiolate ligands that cannot force a square planargeometry. The ligand (L) has some flexibility to change its bite angle via the phenyl-phenyl bond and shouldnot force a planar geometry on its complexes either. Therefore, it is interesting that 2 has adopted a square planarstructure. Complex 2 readily converts to 1 in solution when not in the presence of excess L in a process that ispresumably similar to that known for other mononuclear, bidentate ligated Ni(II) complexes. Both complexes, atleast in the solid state, appear to have an inclination to bind another metal ion on one face of the complex (Ni2+in 1, Na+ in 2). We hope to take advantage of this in future work to synthesize relevant model complexes for theactive sites of the nickel-iron hydrogenases after suitable modifications are made to L.
, a = 13.806(2) Å, b = 14.267(2) Å, c = 16.873(2) Å, =69.263(10), = 69.267(8), = 83.117(10), Z = 2, R1 = 0.0752 (wR2 = 0.2011). (Et4N)(Na·CH3CN)[2]:C34H39N2NaNiS4, triclinic, P, a = 9.9570(10) Å, b = 13.2670(10) Å, c = 13.9560(10) Å, = 108.489(7), = 90.396(6), = 103.570(4), Z = 2, R1 = 0.0390 (wR2 = 0.0995). Both complexes are square planar aboutthe nickel ion in the solid state as well as in solution. Most Ni(II)-thiolate complexes are square planar exceptthe tetrahedral mononuclear complexes with monodentate arylthiolate ligands that cannot force a square planargeometry. The ligand (L) has some flexibility to change its bite angle via the phenyl-phenyl bond and shouldnot force a planar geometry on its complexes either. Therefore, it is interesting that 2 has adopted a square planarstructure. Complex 2 readily converts to 1 in solution when not in the presence of excess L in a process that ispresumably similar to that known for other mononuclear, bidentate ligated Ni(II) complexes. Both complexes, atleast in the solid state, appear to have an inclination to bind another metal ion on one face of the complex (Ni2+in 1, Na+ in 2). We hope to take advantage of this in future work to synthesize relevant model complexes for theactive sites of the nickel-iron hydrogenases after suitable modifications are made to L.