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Development of Ligands and Metal Com...

Sharma, Meenakshi,

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Development of Ligands and Metal Complexes With Weakly Coordinating Apical Elements and Their Application to Nitrene Insertion and Addition to C‒H and C=C Bonds /

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Development of Ligands and Metal Complexes With Weakly Coordinating Apical Elements and Their Application to Nitrene Insertion and Addition to C‒H and C=C Bonds // Meenakshi Sharma.
作者:	Sharma, Meenakshi,
面頁冊數:	1 electronic resource (193 pages)
附註:	Source: Dissertations Abstracts International, Volume: 86-08, Section: B.
Contained By:	Dissertations Abstracts International86-08B.
標題:	Chemistry. -
電子資源:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30989934
ISBN:	9798304910460

Development of Ligands and Metal Complexes With Weakly Coordinating Apical Elements and Their Application to Nitrene Insertion and Addition to C‒H and C=C Bonds /
Sharma, Meenakshi,

Development of Ligands and Metal Complexes With Weakly Coordinating Apical Elements and Their Application to Nitrene Insertion and Addition to C‒H and C=C Bonds /Meenakshi Sharma. - 1 electronic resource (193 pages)

Source: Dissertations Abstracts International, Volume: 86-08, Section: B.

We present a family of triangular coinage metal M3Cl3 complexes [M = Cu (I), Ag (I)] supported by antimony [Sb(III)], and bismuth [Bi(III)]-centered highly basic tetramethyl-guanidinyl [TMG3trphen-E] (E = Sb, Bi) ligand frameworks with their applications as catalysts toward the construction of C‒N bond through aziridination and amination reaction methodologies. The [(TMG3trphen-Sb)Cu3(µ-Cl)3] catalyst gives better yields of aziridines with styrenes than [(TMG3trphen-Bi)Cu3(µ-Cl)3] with PhINTs as a nitrene source. However, the catalytic reactivity of both catalysts is enhanced by an electrophilic nitrene, PhINTces for the amination of C‒H bonds with sec-benzylic substrates. Their non-halogenated copper compounds [(TMG3trphen-E)2Cu2]2+2Y‒ (Y = PF6, B(C6F5)4) have been synthesized by the reaction of TMG3trphen-E ligand with halide-free Cu(I) sources or by dichlorination.Further, the tripodal ligand TMG3trphen-Bz has been synthesized in an electrophilic ligand development for incorporating weakly electron donor apical elements. The ligand possesses a 1,3,5-substituted benzene platform with TMG3trphen arms adopting a pseudo- C3-symmetric geometry. The catalyst [(TMG3trphen-Bz)Cu3(µ-Cl)3] has been subsequently synthesized by extracting a Cu3(-Cl)3 cluster from anhydrous CuCl and shown the reactivity for the amination of sec-benzylic C-H bonds of a panel of substrates. The reactivity of all [(TMG3trphen-E)Cu3(µ-Cl)3] catalysts for amination reactions have also been supported by Hammett analysis which reveals the development of a small positive charge during C-H bond activation.

English

ISBN: 9798304910460Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

Antimony and bismuth ligands

Development of Ligands and Metal Complexes With Weakly Coordinating Apical Elements and Their Application to Nitrene Insertion and Addition to C‒H and C=C Bonds /
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520 $a We present a family of triangular coinage metal M3Cl3 complexes [M = Cu (I), Ag (I)] supported by antimony [Sb(III)], and bismuth [Bi(III)]-centered highly basic tetramethyl-guanidinyl [TMG3trphen-E] (E = Sb, Bi) ligand frameworks with their applications as catalysts toward the construction of C‒N bond through aziridination and amination reaction methodologies. The [(TMG3trphen-Sb)Cu3(µ-Cl)3] catalyst gives better yields of aziridines with styrenes than [(TMG3trphen-Bi)Cu3(µ-Cl)3] with PhINTs as a nitrene source. However, the catalytic reactivity of both catalysts is enhanced by an electrophilic nitrene, PhINTces for the amination of C‒H bonds with sec-benzylic substrates. Their non-halogenated copper compounds [(TMG3trphen-E)2Cu2]2+2Y‒ (Y = PF6, B(C6F5)4) have been synthesized by the reaction of TMG3trphen-E ligand with halide-free Cu(I) sources or by dichlorination.Further, the tripodal ligand TMG3trphen-Bz has been synthesized in an electrophilic ligand development for incorporating weakly electron donor apical elements. The ligand possesses a 1,3,5-substituted benzene platform with TMG3trphen arms adopting a pseudo- C3-symmetric geometry. The catalyst [(TMG3trphen-Bz)Cu3(µ-Cl)3] has been subsequently synthesized by extracting a Cu3(-Cl)3 cluster from anhydrous CuCl and shown the reactivity for the amination of sec-benzylic C-H bonds of a panel of substrates. The reactivity of all [(TMG3trphen-E)Cu3(µ-Cl)3] catalysts for amination reactions have also been supported by Hammett analysis which reveals the development of a small positive charge during C-H bond activation.
546 $a English
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650 4 $a Inorganic chemistry. $3 3173556
650 4 $a Organic chemistry. $3 523952
653 $a Antimony and bismuth ligands
653 $a Aziridination
653 $a C-H amination
653 $a Copper catalysis
653 $a Copper complexes
653 $a Organometallic chemistry
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690 $a 0488
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