Three-Coordinate Halide and Methyl Complexes of Chromium, Manganese, Iron, Cobalt, and Nickel Enabled by an Imidazolin-2-iminato Ligand

被引:0
|
作者
Chen, Guan-Wen [1 ]
Chen, Yu-Hsuan [1 ]
Liu, Hsin-Kuan [2 ]
Lin, Chun-Yi [1 ]
机构
[1] Natl Cheng Kung Univ, Dept Chem, Tainan 701401, Taiwan
[2] Natl Cheng Kung Univ, Core Facil Ctr, Tainan 701401, Taiwan
关键词
COVALENT RADII; REACTIVITY; ANALOGS; CRYSTALLINE; PRECURSORS; OXIDATION; DIVALENT; SINGLE;
D O I
10.1021/acs.organomet.3c00316
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Accessing low-coordinate halide and methyl complexes requires a bulky monodentate or bidentate ligand. Here, the synthesis and characterization of three-coordinate terminal halide and methyl complexes of the first-row transition metals are reported. The halide complexes could be accessed by the reaction of 1 molar equivalent (equiv) of M(II) halides (M = Cr, Mn, Fe, Co, and Ni) and one equiv of the bulky imidazolin-2-iminato ligand NIm(Dipp-) (1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato). Three-coordinate bridging (for Cr) and terminal (for Mn, Fe, and Co) methyl complexes could be synthesized by the reaction of [M(mu(2)-NIm(Dipp))(X)](2) and LiCH3 or CH3MgCl in a 1:2 molar ratio. Single-crystal X-ray diffractometry (SC-XRD) revealed that Mn, Fe, and Co complexes have dimeric structures with terminal methyl ligands in the form of [M(mu(2)-NIm(Dipp))(CH3)](2). In contrast, the Cr analog is a tetranuclear Cr-4 cluster [Cr-4(mu(2)-NIm(Dipp))(2)(mu(2)-CH3)(6)] with both bridging NIm(Dipp) and CH3 ligands. Superconducting quantum interference device (SQUID) magnetometry studies of these methyl complexes showed that the metal ions are antiferromagnetically coupled. Furthermore, the catalytic activities of the methyl complexes and the nickel halide complex were also tested in Kumada cross-coupling reactions, and [Ni(mu(2)-NIm(Dipp))(Cl)](2) was found to be the best catalyst among the complexes.
引用
收藏
页码:2395 / 2404
页数:10
相关论文
共 50 条
  • [1] Electronically unsaturated three-coordinate chloride and methyl complexes of iron, cobalt, and nickel
    Holland, PL
    Cundari, TR
    Perez, LL
    Eckert, NA
    Lachicotte, RJ
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (48) : 14416 - 14424
  • [2] Imidazolin-2-iminato ligand supported titanium(IV) aryloxo complexes - Syntheses and structures
    Naktode, Kishor
    Das, Suman
    Nayek, Hari Pada
    Panda, Tarun K.
    INORGANICA CHIMICA ACTA, 2017, 456 : 24 - 33
  • [3] Imidazolin-2-iminato Ligand-Supported Titanium Complexes as Catalysts for the Synthesis of Urea Derivatives
    Naktode, Kishor
    Das, Suman
    Bhattacharjee, Jayeeta
    Nayek, Hari Pada
    Panda, Tarun K.
    INORGANIC CHEMISTRY, 2016, 55 (03) : 1142 - 1153
  • [4] Isolation of a germanium(II) cation and a germylene iron carbonyl complex utilizing an imidazolin-2-iminato ligand
    Ochiai, Tatsumi
    Franz, Daniel
    Wu, Xiao-Nan
    Inoue, Shigeyoshi
    DALTON TRANSACTIONS, 2015, 44 (24) : 10952 - 10956
  • [5] Electronically unsaturated three-coordinate chloride and methyl complexes of iron, cobalt, and nickel (vol 124, pg 14416, 2002)
    Holland, PL
    Cundari, TR
    Perez, LL
    Eckert, NA
    Lachicotte, RJ
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (38) : 11772 - 11772
  • [6] Ligand dependence of binding to three-coordinate iron(II) complexes
    Chiang, Karen P.
    Barrett, Pamela M.
    Ding, Feizhi
    Smith, Jeremy M.
    Kingsley, Savariraj
    Brennessel, William W.
    Clark, Meghan M.
    Lachicotte, Rene J.
    Holland, Patrick L.
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2009, 238
  • [7] DIFLUOROPHOSPHATE COMPLEXES OF CHROMIUM, MANGANESE, IRON, COBALT, AND NICKEL
    DOVE, MFA
    HIBBERT, RC
    LOGAN, N
    JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1985, (04): : 707 - 710
  • [8] Synthesis and characterization of three-coordinate and related β-diketiminate derivatives of manganese, iron, and cobalt
    Panda, A
    Stender, M
    Wright, RJ
    Olmstead, MM
    Klavins, P
    Power, PP
    INORGANIC CHEMISTRY, 2002, 41 (15) : 3909 - 3916
  • [9] Three-Coordinate Formal Cobalt(0), Iron(0), and Manganese(0) Complexes with Persistent Carbene and Alkene Ligation
    Liu, Yang
    Cheng, Jun
    Deng, Liang
    ACCOUNTS OF CHEMICAL RESEARCH, 2020, 53 (01) : 244 - 254
  • [10] Advances in guanidine ligand design: synthesis of a strongly electron-donating, imidazolin-2-iminato functionalized guanidinate and its properties on iron
    Castillo, Maximiliano
    Barreda, Omar
    Maity, Arnab K.
    Barraza, Brian
    Lu, Jeffrey
    Metta-Magana, Alejandro J.
    Fortier, Skye
    JOURNAL OF COORDINATION CHEMISTRY, 2016, 69 (11-13) : 2003 - 2014