- Synthesis of bridging hydrides of phenyl-functionalized diiron propanedithiolate complexes with 1,2-bis(diphenylphosphine)ethylene or 1,2-bis(diphenylphosphine)ethane ligands
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Abstract Reaction of 2-phenyl-1,3-dibromopropane with in situ generated (μ-SLi)2Fe2(CO)6 yielded a known complex [(μ-SCH2)2CHC6H5]Fe2(CO)6 (A). Displacement of two carbonyls from complex A by cis-1,2-bis(diphenylphosphine)ethylene (dppv) or 1,2-bis(diphenylphosphine)ethane (dppe) in the presence of Me3NO·2H2O gave two chelate complexes [(μ-SCH2)2CHC6H5]Fe2(CO)4(κ 2-dppv), [A(κ 2-dppv)] and [(μ-SCH2)2CHC6H5]Fe2(CO)4(κ 2-dppe), [A(κ 2-dppe)], respectively. Protonation of the diiron centers of [A(κ 2-dppv)] and [A(κ 2-dppe)] using an excess of HBF4·Et2O in dichloromethane at room temperature gave the bridging hydrides [(μ-H)A(κ 2-dppv)]BF4 and [(μ-H)A(κ 2-dppe)]BF4. The complexes [(μ-H)A(κ 2-dppv)]BF4, [A(κ 2-dppe)] and [(μ-H)A(κ 2-dppe)]BF4 were characterized by elemental analysis and spectroscopic methods, and [(μ-H)A(κ 2-dppv)]BF4 and [(μ-H)A(κ 2-dppe)]BF4 were also characterized by X-ray crystallography. The electrochemical behavior of [(μ-H)A(κ 2-dppv)]BF4 was investigated by cyclic voltammetry, and the catalytic electrochemical reduction in protons from trifluoroacetic acid or p-methylbenzene sulfonic acid to give hydrogen was investigated.
- Li, Chang-Gong,Zhang, Gao-Feng,Zhu, Yong,Xue, Feng,Shang, Jing-Yan,Cui, Mao-Jin,Lou, Tian-Jun
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- Copper-Catalyzed Oxyalkynylation of C-S Bonds in Thiiranes and Thiethanes with Hypervalent Iodine Reagents
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We report the oxyalkynylation of thiiranes and thietanes using ethynylbenziodoxolone reagents (EBXs) to readily access functionalized building blocks bearing an alkynyl, a benzoate, and an iodide group. The reaction proceeds with high atom efficiency most
- Borrel, Julien,Pisella, Guillaume,Waser, Jerome
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supporting information
p. 422 - 427
(2020/01/31)
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- Diverse ring opening of thietanes and other cyclic sulfides: An electrophilic aryne activation approach
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Organosulfides are a common class of structure units in bioactive molecules and functional materials motivating continuous developments of efficient synthetic methods. Herein, we report an electrophilic aryne-activated ring opening protocol of one or two
- Zheng, Tianyu,Tan, Jiajing,Fan, Rong,Su, Shuaisong,Liu, Binbin,Tan, Chen,Xu, Kun
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supporting information
p. 1303 - 1306
(2018/02/14)
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- Haloalkane dehalogenase catalysed desymmetrisation and tandem kinetic resolution for the preparation of chiral haloalcohols
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Six different bacterial haloalkane dehalogenases were recombinantly produced in Escherichia coli, purified, and used to catalyse the conversion of prochiral short-chain dihaloalkanes and a meso dihaloalkane, yielding enantioenriched haloalcohols. A two-reaction one-enzyme process was established in which the desymmetrisation of a dihaloalkane is followed by kinetic resolution of the chiral haloalcohol that is produced in the first step. In case of 1,3-dibromo-2-methylpropane and 1,3-dibromo-2-phenylpropane, an increase of the enantiomeric excess of the respective haloalcohol was observed in time, leading to ee values of >97%, with analytical yields of 24 and 52%, respectively. The results show that haloalkane dehalogenases can be used for the production of highly enantioenriched haloalcohols and that in some cases product enantiopurity can be improved by allowing a two-step one-enzyme tandem reaction.
- Westerbeek, Alja,Van Leeuwen, Jan G.E.,Szymański, Wiktor,Feringa, Ben L.,Janssen, Dick B.
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experimental part
p. 7645 - 7650
(2012/09/21)
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