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Arene exchange accelerated by a pendant ligand.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Arene exchange accelerated by a pendant ligand.
作者:	Chlenov, Anatoli.
面頁冊數:	307 p.
附註:	Adviser: M. F. Semmelhack.
附註:	Source: Dissertation Abstracts International, Volume: 64-01, Section: B, page: 0209.
Contained By:	Dissertation Abstracts International64-01B.
標題:	Chemistry, Organic.
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3078621
ISBN:	049399498X

Arene exchange accelerated by a pendant ligand.
Chlenov, Anatoli.

Arene exchange accelerated by a pendant ligand. [electronic resource] - 307 p.

Adviser: M. F. Semmelhack.

Thesis (Ph.D.)--Princeton University, 2003.

Modification of the tri(pyrrolyl)phosphine with a properly designed pendant side chain allows arene exchange in (arene)Cr(CO)2(phosphine) to occur at room temperature. Temporary coordination of the side chain in the partially dissociated arene intermediate is proposed to be responsible for the mild reaction conditions. A series of (2-substituted-pyrrolyl)dipyrrolylphosphines was synthesized and the effect of the side chain on the arene exchange rate was systematically evaluated. Arene exchange in (arene)Cr(CO)2((2-methylcarboxypyrrolyl)dipyrrolylphosphine) was investigated for a variety of incoming and leaving arenes. An interchange mechanism is proposed where the transition state occurs on the way from eta 2-arene chromium complex to eta2-arene' chromium complex, where arene' is an incoming arene. The mechanism was substantiated computationally by calculating the Hartree-Fock energies (3-21G(*) basis set) of the intermediates involved.

ISBN: 049399498XSubjects--Topical Terms:

193634
Chemistry, Organic.

Arene exchange accelerated by a pendant ligand.
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500 $a Source: Dissertation Abstracts International, Volume: 64-01, Section: B, page: 0209.
502 $a Thesis (Ph.D.)--Princeton University, 2003.
520 # $a Modification of the tri(pyrrolyl)phosphine with a properly designed pendant side chain allows arene exchange in (arene)Cr(CO)2(phosphine) to occur at room temperature. Temporary coordination of the side chain in the partially dissociated arene intermediate is proposed to be responsible for the mild reaction conditions. A series of (2-substituted-pyrrolyl)dipyrrolylphosphines was synthesized and the effect of the side chain on the arene exchange rate was systematically evaluated. Arene exchange in (arene)Cr(CO)2((2-methylcarboxypyrrolyl)dipyrrolylphosphine) was investigated for a variety of incoming and leaving arenes. An interchange mechanism is proposed where the transition state occurs on the way from eta 2-arene chromium complex to eta2-arene' chromium complex, where arene' is an incoming arene. The mechanism was substantiated computationally by calculating the Hartree-Fock energies (3-21G(*) basis set) of the intermediates involved.
520 # $a Several novel aspects of arene chromium chemistry are described. Selective double substitution by amine nucleophiles on (difluorobenzene)Cr(CO) 3 is reported. Replacement of one of the carbonyl ligands by an (N-methylbenzylamine)dipyrrolyl-phosphine retards the nucleophilic aromatic substitution reaction only to a small extent. The phosphine ligand can be generated on the solid phase to allow attachment of the arene via an activating chromium unit as a traceless linker.
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