Synthesis and Characterization of Bioinspired [Mo2Fe2]-Hydride Cluster Complexes and Their Application in the Catalytic Silylation of N2

被引：30

作者：

Ohki, Yasuhiro ^{[1
,2
]}

Araki, Yuna ^{[1
,2
]}

Tada, Mizuki ^{[1
,2
,3
,4
]}

Sakai, Yoichi ^{[5
]}

机构：

[1] Nagoya Univ, Grad Sch Sci, Dept Chem, Chikusa Ku, Furo Cho, Nagoya, Aichi 4648602, Japan

[2] Nagoya Univ, Res Ctr Mat Sci, Chikusa Ku, Furo Cho, Nagoya, Aichi 4648602, Japan

[3] Nagoya Univ, RCMS, Chikusa Ku, Furo Cho, Nagoya, Aichi 4648602, Japan

[4] Nagoya Univ, IRCCS, Chikusa Ku, Furo Cho, Nagoya, Aichi 4648602, Japan

[5] Daido Univ, Dept Chem, Minami Ku, Takiharu Cho, Nagoya, Aichi 4578530, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2017年 / 23卷 / 53期

基金：

日本科学技术振兴机构;

关键词：

cluster compounds; iron; hydride ligands; molybdenum; reduction; PNEUMONIAE NITROGENASE ACTION; AMBIENT REACTION CONDITIONS; CRYSTAL-STRUCTURES; STRUCTURAL-CHARACTERIZATION; HETEROMETALLIC CLUSTERS; SUBSTITUTION-REACTIONS; POLYHYDRIDE COMPLEXES; MOLECULAR DINITROGEN; THIOLATE COMPLEXES; HYDRIDE COMPLEXES;

D O I：

10.1002/chem.201702925

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The hydride-supported [Mo2Fe2] cluster complex {Cp*Mo(PMe3)}(2){FeN(SiMe3)(2)}(2)(H)(8) (2a; Cp* = eta(5)-C5Me5) and its [Mo2Mn2] congener 2b were synthesized from the reactions of Cp*Mo(PMe3)(H)(5) (1) with M{N(SiMe3)(2)}(2) (M = Fe, Mn). The amide-to-thiolate ligand-exchange reactions of complex 2a with bulky thiol reagents (HSR; R = 2,4,6-iPr(3)C(6)H(2) (Tip), 2,6-(SiMe3)(2)C6H3 (Btp)) furnished the corresponding hydride-supported [Mo2Fe2](SR)(2) cluster complexes. The [Mo2Fe2] clusters served as catalyst precursors for the reductive silylation of N-2 and yielded approximate to 65-69equivalents of N(SiMe3)(3) relative to the [Mo2Fe2] clusters. Treatment of complexes 2a and b with an excess of CNtBu resulted in the formation of dinuclear Mo-Fe and Mo-Mn complexes, which indicated that the [Mo2M2] cores (M = Fe, Mn) split into two dinuclear species upon accommodation of substrates.

引用

页码：13240 / 13248

页数：9

共 78 条

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