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A Rearrangement of Azobenzene upon Interaction with an Aluminum( I ) Monomer LAl {L = HC[(CMe)(NAr)] 2 , Ar = 2,6‐ i Pr 2 C 6 H 3 }
Author(s) -
Zhu Hongping,
Chai Jianfang,
Fan Hongjun,
Roesky Herbert W.,
Nehete Umesh N.,
Schmidt HansGeorg,
Noltemeyer Mathias
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400922
Subject(s) - chemistry , azobenzene , monomer , cycloaddition , medicinal chemistry , activation barrier , stereochemistry , activation energy , ring (chemistry) , crystallography , molecule , polymer , organic chemistry , catalysis
Reaction of LAl ( 1 ) or [LAl{η 2 ‐C 2 (SiMe 3 ) 2 }] ( 2 ) {L = HC[(CMe)(NAr)] 2 , Ar = 2,6‐ i Pr 2 C 6 H 3 } with azobenzene affords a five‐membered ring compound [LAl{N(H)‐ o ‐C 6 H 4 N(Ph)}] ( 3 ). In the formation of 3 a three‐membered intermediate [LAl(η 2 ‐N 2 Ph 2 )] ( A ) is suggested by a [1 + 2] cycloaddition reaction; A is not stable and further rearranges to 3 . DFT calculations on similar compounds with modified L' {L' = HC[(CMe)(NPh)] 2 } show that the complexation energy of the reaction of L'Al with azobenzene to form [L'Al(η 2 ‐N 2 Ph 2 )] is about–39 kcal mol –1 , and the best estimate of the energy difference between [L'Al(η 2 ‐N 2 Ph 2 )] and [L'Al{N(H)‐ o ‐C 6 H 4 N(Ph)}] is–76 kcal mol –1 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)