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N-heterocyclic carbenes: Rhodium and...

Chianese, Anthony R.

N-heterocyclic carbenes: Rhodium and iridium complexes, abnormal binding modes, carbon-carbon cleavage reactions, and asymmetric catalysis.

Record Type:	Electronic resources : Monograph/item
Title/Author:	N-heterocyclic carbenes: Rhodium and iridium complexes, abnormal binding modes, carbon-carbon cleavage reactions, and asymmetric catalysis.
Author:	Chianese, Anthony R.
Description:	130 p.
Notes:	Director: Robert H. Crabtree.
Notes:	Source: Dissertation Abstracts International, Volume: 66-11, Section: B, page: 5971.
Contained By:	Dissertation Abstracts International66-11B.
Subject:	Chemistry, Inorganic.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3194635
ISBN:	9780542393013

N-heterocyclic carbenes: Rhodium and iridium complexes, abnormal binding modes, carbon-carbon cleavage reactions, and asymmetric catalysis.
Chianese, Anthony R.

N-heterocyclic carbenes: Rhodium and iridium complexes, abnormal binding modes, carbon-carbon cleavage reactions, and asymmetric catalysis. - 130 p.

Director: Robert H. Crabtree.

Thesis (Ph.D.)--Yale University, 2005.

This dissertation concerns the synthesis and properties of NHC (N-heterocyclic carbene) ligands and their derived transition metal complexes. Chapter two describes the synthesis of rhodium and iridium complexes of NHCs via transmetalation from silver. The free energy barrier for rotation about the metal-carbon bond is measured, and a measure of the electron donor strength of NHCs using infrared spectroscopy is presented. NHCs are found to be significantly more electron donating than tertiary phosphines. In chapter three, the effect of ligand geometry on the preference for chelated vs. dinuclear binding of NHCs to rhodium is explored. Chapter four describes the synthesis and electronic properties of abnormal C4(5)-bound NHCs, and their derived iridium complexes. Abnormal NHCs are found to be even more electron-donating than normal NHCs. Chapter five details studies of an unexpected reaction of 2-substituted imidazolium salts with silver oxide to give normal silver-NHC complexes, via an oxidative carbon-carbon bond cleavage. Chapter six describes the synthesis of chiral bidentate NHC ligands derived from 2,2'-diamino-1,1'-binaphthyl. The syntheses of rhodium and iridium complexes, and their application to the asymmetric hydrosilylation of acetophenone, are described.

ISBN: 9780542393013Subjects--Topical Terms:

197298
Chemistry, Inorganic.

N-heterocyclic carbenes: Rhodium and iridium complexes, abnormal binding modes, carbon-carbon cleavage reactions, and asymmetric catalysis.
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245 1 0 $a N-heterocyclic carbenes: Rhodium and iridium complexes, abnormal binding modes, carbon-carbon cleavage reactions, and asymmetric catalysis.
300 $a 130 p.
500 $a Director: Robert H. Crabtree.
500 $a Source: Dissertation Abstracts International, Volume: 66-11, Section: B, page: 5971.
502 $a Thesis (Ph.D.)--Yale University, 2005.
520 # $a This dissertation concerns the synthesis and properties of NHC (N-heterocyclic carbene) ligands and their derived transition metal complexes. Chapter two describes the synthesis of rhodium and iridium complexes of NHCs via transmetalation from silver. The free energy barrier for rotation about the metal-carbon bond is measured, and a measure of the electron donor strength of NHCs using infrared spectroscopy is presented. NHCs are found to be significantly more electron donating than tertiary phosphines. In chapter three, the effect of ligand geometry on the preference for chelated vs. dinuclear binding of NHCs to rhodium is explored. Chapter four describes the synthesis and electronic properties of abnormal C4(5)-bound NHCs, and their derived iridium complexes. Abnormal NHCs are found to be even more electron-donating than normal NHCs. Chapter five details studies of an unexpected reaction of 2-substituted imidazolium salts with silver oxide to give normal silver-NHC complexes, via an oxidative carbon-carbon bond cleavage. Chapter six describes the synthesis of chiral bidentate NHC ligands derived from 2,2'-diamino-1,1'-binaphthyl. The syntheses of rhodium and iridium complexes, and their application to the asymmetric hydrosilylation of acetophenone, are described.
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773 0 # $g 66-11B. $t Dissertation Abstracts International
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790 1 0 $a Crabtree, Robert H., $e advisor
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