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Reactions of the Aluminum( I ) Monomer LAl [L = HC{(CMe)(NAr)} 2 ; Ar = 2,6‐ i Pr 2 C 6 H 3 ] with Imidazol‐2‐ylidene and Diphenyldiazomethane. A Hydrogen Transfer from the L Ligand to the Central Aluminum Atom and Formation of the Diiminylaluminum Compound LAl(N=CPh 2 ) 2
Author(s) -
Zhu Hongping,
Chai Jianfang,
Stasch Andreas,
Roesky Herbert W.,
Blunck Torsten,
Vidovic Denis,
Magull Jörg,
Schmidt HansGeorg,
Noltemeyer Mathias
Publication year - 2004
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.200400159
Subject(s) - chemistry , adduct , carbene , ligand (biochemistry) , yield (engineering) , monomer , solid state , medicinal chemistry , hydrogen bond , crystallography , stereochemistry , molecule , organic chemistry , polymer , catalysis , biochemistry , materials science , receptor , metallurgy
Abstract The solid‐state reaction of LAl and imidazol‐2‐ylidene at elevated temperature (120 °C) yielded the aluminum monohydride N ‐heterocyclic carbene adduct [{HC[C(CH 2 )NAr] (CMeNAr)}AlH‐{CN(R)C 2 Me 2 N(R)}] [R = i Pr ( 1 ), Me ( 2 )]. Compounds 1 and 2 have been characterized by spectroscopic (IR, and 1 H and 13 C NMR), mass spectrometric, and elemental analyses, and 1 was further characterized by X‐ray structural analysis. These experimental data indicate that the Al−H bond is formed by hydrogen migration from one of the methyl groups of the β‐diketiminato ligand backbone. The reaction of LAl with two equivalents of diphenyldiazomethane afforded the diiminylaluminum compound LAl(N=CPh 2 ) 2 ( 3 ), while an excess of diphenyldiazomethane resulted in the formation of Ph 2 C=N−N=CPh 2 . This suggests that Ph 2 C=N−N=CPh 2 is initially generated and then reacts further by oxidative addition to yield 3 . The X‐ray structural analysis reveals that compound 3 contains the shortest Al−N iminyl bond among those with a four‐coordinate aluminum center. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)