TY - JOUR
T1 - Five-coordinate aluminum bromides
T2 - Synthesis, structure, cation formation, and cleavage of phosphate ester bonds
AU - Mitra, Amitabha
AU - DePue, Lauren J.
AU - Parkin, Sean
AU - Atwood, David A.
PY - 2006/2/1
Y1 - 2006/2/1
N2 - The alkane elimination reaction between Salen(tBu)H2 ligands and diethylaluminum bromide was used to prepare three Salen aluminum bromide compounds salen(tBu)AlBr (1) (salen = N,N′-ethylenebis- (3,5-di-tert-butylsalicylideneimine)), salpen(tBu)AlBr (2) (salpen = N,N′-propylenebis(3,5-di-tert-butylsalicylideneimine)), and salophen( tBu)AlBr (3) (salophen = N,N′-o-phenylenenebis(3,5-di-tert- butylsalicylideneimine)). The compounds contain five-coordinate aluminum either in a distorted square pyramidal or a trigonal bipyramidal environment. The bromide group in these compounds could be displaced by triphenylphosphine oxide or triphenyl phosphate to produce the six-coordinate cationic aluminum compounds [salen(tBu)Al(Ph3PO)2]Br (4), [salpen( tBu)Al(Ph3PO)2]Br (5), [salophen( tBu)Al(Ph3PO)2]Br (6), and [salophen-( tBu)Al{(PhO)3PO)}2]Br (7). All the compounds were characterized by 1H, 13C, 27Al, and 31P NMR, IR, mass spectrometry, and melting point. Furthermore, compounds 1-3 and 5-7 were structurally characterized by single-crystal X-ray diffraction. Compounds 1-3 dealkylated a series of organophosphates in stoichiometric reactions by breaking the ester C-O bond. Also, they were catalytic in the dealkylation reaction between trimethyl phosphate and added boron tribromide.
AB - The alkane elimination reaction between Salen(tBu)H2 ligands and diethylaluminum bromide was used to prepare three Salen aluminum bromide compounds salen(tBu)AlBr (1) (salen = N,N′-ethylenebis- (3,5-di-tert-butylsalicylideneimine)), salpen(tBu)AlBr (2) (salpen = N,N′-propylenebis(3,5-di-tert-butylsalicylideneimine)), and salophen( tBu)AlBr (3) (salophen = N,N′-o-phenylenenebis(3,5-di-tert- butylsalicylideneimine)). The compounds contain five-coordinate aluminum either in a distorted square pyramidal or a trigonal bipyramidal environment. The bromide group in these compounds could be displaced by triphenylphosphine oxide or triphenyl phosphate to produce the six-coordinate cationic aluminum compounds [salen(tBu)Al(Ph3PO)2]Br (4), [salpen( tBu)Al(Ph3PO)2]Br (5), [salophen( tBu)Al(Ph3PO)2]Br (6), and [salophen-( tBu)Al{(PhO)3PO)}2]Br (7). All the compounds were characterized by 1H, 13C, 27Al, and 31P NMR, IR, mass spectrometry, and melting point. Furthermore, compounds 1-3 and 5-7 were structurally characterized by single-crystal X-ray diffraction. Compounds 1-3 dealkylated a series of organophosphates in stoichiometric reactions by breaking the ester C-O bond. Also, they were catalytic in the dealkylation reaction between trimethyl phosphate and added boron tribromide.
UR - https://www.scopus.com/pages/publications/31944433890
UR - https://www.scopus.com/inward/citedby.url?scp=31944433890&partnerID=8YFLogxK
U2 - 10.1021/ja054684s
DO - 10.1021/ja054684s
M3 - Article
C2 - 16433530
AN - SCOPUS:31944433890
SN - 0002-7863
VL - 128
SP - 1147
EP - 1153
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 4
ER -