New Class of Hydrido Iron(II) Compounds with cis-Reactive Sites: Combination of Iron and Diphosphinodithio Ligand

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• 作者：Jianguo Liu ; Fanjun Zhang ; Ailing Zhang ; Prof. Dr. Qingxiao Tong ; Prof. Dr. Chen-Ho Tung and Prof. Dr. Wenguang Wang
• 刊名：Chemistry – An Asian Journal
• 出版年：2016
• 出版时间：August 19, 2016
• 年：2016
• 卷：11
• 期：16
• 页码：2271-2277
• 全文大小：948K
• ISSN：1861-471X

文摘

The cationic complex [Fe(P₂S₂)(NCMe)₂]²⁺ (P₂S₂=(Ph₂PC₆H₄CH₂S)₂(C₂H₄) ([1(NCMe)₂]²⁺)), with two MeCN ligands in a cis orientation, was synthesized and characterized. The MeCN ligand in [1(NCMe)₂]²⁺ undergoes further substitution by a hydride ligand or CO to give iron(II) hydrides [H1(NCMe)]⁺, [H1H]⁰, and [H1(CO)]⁺. The order of reactivity of the hydrides was [H1H]⁰>[H1(NCMe)]⁺>[H1(CO)]⁺, and was illustrated by their reactions toward protic acids, the organic cation of 10-methylacridinium (MeAcr⁺) as a hydride acceptor, and intermolecular hydride transfer reactions among these ferrous compounds. For example, MeAcr⁺ was reduced initially by a one-electron transfer process from [H1H]⁰, resulting in competing reactions of MeAcr^. dimerization, hydrogen atom transfer from [H1H]⁺ to MeAcr^., and decomposition of [H1H]⁺. MeAcrH was produced in excellent yields through a single-step H⁻ transfer from [H1(NCMe)]⁺ to MeAcr⁺, but [H1(CO)]⁺ was inactive toward MeAcr⁺.