Efficient Catalytic Conversion of Dinitrogen to N(SiMe3)3 Using a Homogeneous Mononuclear Cobalt Complex
Efficient Catalytic Conversion of Dinitrogen to N(SiMe3)3 Using a Homogeneous Mononuclear Cobalt Complex
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使用均质单核钴络合物将二氮高效催化转化为 N(SiMe3)3
DOI：
10.1021/acscatal.7b04351
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发表时间：
2018
期刊：
影响因子：
12.9
通讯作者：
Masuda Hideki
中科院分区：
文献类型：
--
作者：
Suzuki Tatsuya;Fujimoto Keisuke;Takemoto Yoshiyuki;Wasada-Tsutsui Yuko;Ozawa Tomohiro;Inomata Tomohiko;Fryzuk Michael D.;Masuda Hideki
将三齿膦-烯酰胺亚氨基膦结合到钴（II）上产生四面体Co（NpNPiPr）Cl，1，其在二氮下还原时产生T形顺磁性Co（I）络合物Co（NpNPiPr），2。该顺磁性T形衍生物与顺磁性二氮衍生物Co（NpNPiPr）（N2），3处于平衡状态，其可通过IR和低温UV-vis光谱检测。1和2作为均相催化剂，用于在过量的KCl 8和Me 3SiCl存在下在低温下将分子氮转化为三（三甲基硅烷基）胺（N（SiMe 3）3）（约200当量，水解后定量为NH 4Cl）。
Incorporation of the tridentate phosphine-enamidoiminophosphorane onto cobalt(II) produces tetrahedral Co(NpNPiPr)Cl,1, which upon reduction under dinitrogen generates the T-shaped, paramagnetic Co(I) complex Co(NpNPiPr),2. This paramagnetic T-shaped derivative is in equilibrium with the paramagnetic dinitrogen derivative Co(NpNPiPr)(N2),3, which can be detected by IR and low-temperature UV–vis spectroscopy. Both1and2act as homogeneous catalysts for the conversion of molecular nitrogen into tris(trimethylsilyl)amine (N(SiMe3)3) (∼200 equiv, quantified as NH4Cl after hydrolysis) in the presence of excess KC8and Me3SiCl at low temperatures.