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Normal and abnormal binding in N-het...

Kovacevic, Anes.

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Normal and abnormal binding in N-heterocyclic carbene complexes.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Normal and abnormal binding in N-heterocyclic carbene complexes./
Author:	Kovacevic, Anes.
Description:	100 p.
Notes:	Source: Dissertation Abstracts International, Volume: 65-03, Section: B, page: 1318.
Contained By:	Dissertation Abstracts International65-03B.
Subject:	Chemistry, Inorganic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3125235
ISBN:	0496725254

Normal and abnormal binding in N-heterocyclic carbene complexes.
Kovacevic, Anes.

Normal and abnormal binding in N-heterocyclic carbene complexes. - 100 p.

Source: Dissertation Abstracts International, Volume: 65-03, Section: B, page: 1318.

Thesis (Ph.D.)--Yale University, 2004.

Novel heterocyclic carbene complexes obtained from reactions of their imidazolium salt ligand precursors with Pd2(dba)3 and Ir(H)5(PPh3)2 are discussed in this dissertation.

ISBN: 0496725254Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Normal and abnormal binding in N-heterocyclic carbene complexes.
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100 1 $a Kovacevic, Anes. $3 1932496
245 1 0 $a Normal and abnormal binding in N-heterocyclic carbene complexes.
300 $a 100 p.
500 $a Source: Dissertation Abstracts International, Volume: 65-03, Section: B, page: 1318.
500 $a Director: Robert H. Crabtree.
502 $a Thesis (Ph.D.)--Yale University, 2004.
520 $a Novel heterocyclic carbene complexes obtained from reactions of their imidazolium salt ligand precursors with Pd2(dba)3 and Ir(H)5(PPh3)2 are discussed in this dissertation.
520 $a Chapter 2 shows how oxidative addition can be successfully used to synthesize N-heterocyclic carbene complexes. Oxidative addition is operationally simple, has very good atom economy, avoids strong bases like BuLi or NaH and reduces the number of steps needed to prepare desired complexes. This chapter deals with the application of oxidative addition reactions of imidazolium salts [Py-C3H3N2-R]BF4 and a Pd(0) source to give new biscarbene complexes (Py = 2-pyridyl; R = Me, i-Pr, Mesityl).
520 $a Oxidative addition is further explored in Chapter 3. A new organometallic structure, the abnormal carbene, is synthesized from pyridine functionalized imidazolium salts of typical formula [Py-CH2-C3H 3N2-R]BF4. In this type of complex the metal is bound to the backbone C4 position instead of the usual imidazole C2 position. Complete characterization of the abnormal and normal carbenes includes an X-ray study. Some mechanistic investigations are also discussed.
520 $a Chapter 4 continues to investigate the reaction of [Py-C3H 3N2-R]BF4 with Ir(H)5(PPh3) 2, by looking at an unexpected intermediate. This is another novel class of organometallic species with a fully hydrogenated ring, that upon further heating transforms into the abnormal carbene. Mechanistic investigation, including deuteration experiments, showed that two ligand precursors [Py-C3H 3N2-R]BF4 and [Py-CH2-C 3H3N2-R]BF4 react by different mechanisms to give analogous abnormal carbene complexes.
520 $a The next chapter deals with another interesting variable in the reactions of imidazolium salts with Ir(H)5(PPh3)2: a novel counterion effect. With Br as the counterion, the normal carbene is preferentially formed, but with SbF6 as counterion, the abnormal carbene is formed.
590 $a School code: 0265.
650 4 $a Chemistry, Inorganic. $3 517253
690 $a 0488
710 2 0 $a Yale University. $3 515640
773 0 $t Dissertation Abstracts International $g 65-03B.
790 1 0 $a Crabtree, Robert H., $e advisor
790 $a 0265
791 $a Ph.D.
792 $a 2004
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3125235