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Normal and abnormal binding in N-heterocyclic carbene complexes

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Normal and abnormal binding in N-heterocyclic carbene complexes
作者:	Kovacevic, Anes.
面頁冊數:	100 p.
附註:	Director: Robert H. Crabtree.
附註:	Source: Dissertation Abstracts International, Volume: 65-03, Section: B, page: 1318.
Contained By:	Dissertation Abstracts International65-03B.
標題:	Chemistry, Inorganic.
電子資源:	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 [electronic resource] - 100 p.

Director: Robert H. Crabtree.

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

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).

ISBN: 0496725254Subjects--Topical Terms:

197298
Chemistry, Inorganic.

Normal and abnormal binding in N-heterocyclic carbene complexes
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502 $a Thesis (Ph.D.)--Yale University, 2004.
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 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 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 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 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.
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790 1 0 $a Crabtree, Robert H., $e advisor
791 $a Ph.D.
792 $a 2004
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