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A Methylene‐Bridged Dialuminium Compound as a Chelating Lewis Acid: Complexation of Nitrite and Nitrate Anions by R 2 Al–CH 2 –AlR 2 [R = CH(SiMe 3 ) 2 ] ☆
Author(s) -
Uhl Werner,
Hannemann Frank,
Saak Wolfgang,
Wartchow Rudolf
Publication year - 1998
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/(sici)1099-0682(199807)1998:7<921::aid-ejic921>3.0.co;2-5
Subject(s) - chemistry , nitrite , medicinal chemistry , lewis acids and bases , methylene , chelation , inorganic chemistry , derivative (finance) , crystal structure , sodium nitrite , lithium nitrate , nitrate , ion , crystallography , organic chemistry , catalysis , ionic bonding , financial economics , economics
Sodium nitrite (NaNO 2 ) dissolves readily in THF, when the methylene‐bridged dialuminium compound R 2 Al–CH 2 –AlR 2 [R = CH(SiMe 3 ) 2 ] 1 with two coordinatively unsaturated aluminium atoms is added. Compound 1 reacts as a chelating Lewis acid, and, as shown by a crystal structure deter‐mination of the [Na([18]crown‐6)(Et 2 O)] + derivative 5c , a compound ( 5 ) is formed, in which one oxygen atom and the nitrogen atom of the nitrite ion are each coordinated by one aluminium atom to form a five‐membered Al 2 CNO hetero‐cycle. The second oxygen atom of the nitrite anion is not affected. Similarly, lithium nitrate (LiNO 3 ) reacts with 1 to yield a THF soluble product ( 6a ). Single crystals were obtain‐ed of the [Li( N,N′,N′′ ‐trimethyltriazinane) 2 ] + derivative 6c , whose structure shows each aluminium atom to be coordinated by one oxygen atom of the nitrate ion to give a six‐membered Al 2 CNO 2 heterocycle.