NHC supported CuI amido and sulfido complexes: Synthesis, characterization, and applications in small molecule activation.

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Bibliographic Details
Author / Creator:Zhai, Junjie.
Description:186 p.
Format: E-Resource Dissertations
Local Note:School code: 0330.
URL for this record:http://pi.lib.uchicago.edu/1001/cat/bib/10168510
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Other authors / contributors:University of Chicago.
Notes:Advisor: Michael D. Hopkins.
Thesis (Ph.D.)--The University of Chicago, Division of the Physical Sciences, Department of Chemistry, 2015.
Dissertation Abstracts International, Volume: 76-08(E), Section: B.
Summary:This thesis presents the synthesis and characterization of several new Cu(I) amido and sulfido complexes supported by N-Heterocyclic Carbene (NHC) ligand and discusses their applications in small molecule activation, e.g. CO2 activation, etc..
Chapter 1 briefly discusses the NHC ligand, focusing on the preparation, electronic and steric properties and applications in NHC-Cu complexes. The synthesis of (IPr)CuCl (IPr = 1,3-di(2,6-di-isopropylphenyl)-imidazolin-2-ylidene) is described. It serves as a good starting material to prepare a variety of NHC-CuI complexes, e.g. IPr-Cu amido and sulfido complexes, etc..
Chapter 2 describes the synthesis and characterization of (IPr)Cu{N( p-C6H4R)2} (R = NMe2, OCH3 , H and CF3) complexes. They react reversibly with CO 2 to afford (IPr)Cu{OC(O)N(p-C6H4R) 2}. The equilibrium can be effectively tuned by temperature and the R substituents in the amido ligand. Low temperature and electron-donating R groups facilitate the formation of carbamato product.
Chapter 3 examines the mechanism of the reaction of (IPr)Cu{N(SiMe 3)2} with CO2 that affords (IPr)Cu(NCO) complex. Two reaction intermediates, (IPr)Cu(OSiMe3) and Me3SiNCO, have been discovered. Silyl group migration from the nitrogen atom to the oxygen is proposed as the key step in the reaction mechanism. The synthesis and characterization of (IPr)Cu{N(R)(SiMe3)} (R = Ph, t Bu) complexes is also reported. They react with CO2 to give (IPr)Cu{N(R){C(O)OSiMe3}} complexes.
Chapter 4 focuses on the synthesis and characterization of novel [{(IPr)Cu} 3(u3-S)][BF4] and {(IPr*)Cu}2(mu-S) complexes. Intermolecular Me3SiF elimination from (NHC)CuF and Cu-SSiMe 3 complexes has been used to approach the Cu-S clusters. The reaction of {(IPr*)Cu}2(mu-S) with BnX (X = Cl, Br) forms (IPr*)CuX and (IPr*)Cu(SBn). Treatment of {(IPr*)Cu}2(mu-S) with dibromo alkanes affords (IPr*)CuBr and cyclic thioethers.