title: Self-assembly and redox modulation of the cavity size of an unusual rectangular iron thiolate aryldiisocyanide metallocyclophane.
abstract: The decarbonylation reaction of ferric carbonyl dicationic [Cp(2)Fe(2)(μ-SEt)(2)(CO)(2)](BF(4))(2) [1(BF(4))(2)] carried out in refluxing acetonitrile affords a binuclear iron-sulfur core complex [Cp(2)Fe(2)(μ-SEt)(2)(CH(3)CN)(2)](BF(4))(2) [2(BF(4))(2)] containing two acetonitrile coordinated ligands. The treatment of 2(BF(4))(2) with 2 equiv of the 1,4-diisocyanobenzene (1,4-CNC(6)H(4)NC) results in the formation of the diisocyanide complex [Cp(2)Fe(2)(μ-SEt)(2)(1,4-CNC(6)H(4)NC)(2)](BF(4))(2) [3(BF(4))(2)]. The rectangular tetranuclear iron thiolate aryldiisocyanide metallocyclophane complex [Cp(4)Fe(4)(μ-SEt)(4)(μ-1,4-CNC(6)H(4)NC)(2)](BF(4))(4) [4(BF(4))(4)] has been synthesized by a self-assembly reaction between equimolar amounts of 2(BF(4))(2) and 1,4-diisocyanobenzene or by a stepwise route involving mixing of a 1:1 molar ratio of complexes 2(BF(4))(2) and 3(BF(4))(2). Chemical reduction of 4(BF(4))(4) by KC(8) was observed to produce the reduction product 4(BF(4))(2). The spectroscopic and electrochemical properties of the iron-sulfur core complexes 1(PF(6))(2), 3(BF(4))(2), 4(BF(4))(4), and 4(BF(4))(2) were determined. Finally, differences between the redox control cavities of rectangular tetranuclear iron thiolate aryldiisocyanide complexes are revealed by a comparison of the X-ray crystallographically determined structures of complexes 4(BF(4))(4) and 4(BF(4))(2).
authors: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 807, Taiwan.
authors: Pei-Chin
authors: PC
authors: Lin
authors: Hsing-Yin
authors: HY
authors: Chen
authors: Po-Yu
authors: PY
authors: Chen
authors: Ming-Hsi
authors: MH
authors: Chiang
authors: Michael Y
authors: MY
authors: Chiang
authors: Ting-Shen
authors: TS
authors: Kuo
authors: Sodio C N
authors: SC
authors: Hsu
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D001555:Benzene Derivatives / Q000737:chemistry; D001665:Binding Sites; D001896:Boron Compounds / Q000737:chemistry; D015393:Chemistry, Bioinorganic / Q000379:methods*; D018360:Crystallography, X-Ray; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008667:Metalloproteins / Q000032:analysis / Q000138:chemical synthesis*; D008958:Models, Molecular; D008968:Molecular Conformation; D018716:Molecular Mimicry; D009570:Nitriles / Q000737:chemistry; D009942:Organometallic Compounds / Q000032:analysis / Q000138:chemical synthesis*; D010084:Oxidation-Reduction; D013438:Sulfhydryl Compounds / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry*
chemical_list: C554961:1,4-diisocyanobenzene; D000097:Acetonitriles; D001555:Benzene Derivatives; D001896:Boron Compounds; D008024:Ligands; D008667:Metalloproteins; D009570:Nitriles; D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D013455:Sulfur; D007501:Iron; C032159:acetonitrile