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Heteronuclear Alkoxide Compounds Containing Copper and Alkaline Earth Metals

1993; Wiley; Volume: 76; Issue: 1 Linguagem: Inglês

10.1002/hlca.19930760139

1522-2675

Woflgang Bidell, H. William Bosch, Dario Veghini, Hans‐Ulrich Hund, J. Döring, Heinz Berke,

Layered Double Hydroxides Synthesis and Applications

Abstract The tetrameric Cu(β‐diketonate) alkoxide complex [Cu(thd)(OCH 2 CH 2 OCH 3 )] 4 (thd = 2,2,6,6‐tetramethyl‐3,5‐heptanedionate; 1a ) reacts with the alkaline earth metal alkoxides [M(OCH 2 CH 2 OCH 3 ) 2 ] (M = Ca, 2a ; M = Sr, 2b ; M = Ba, 2c ) to yield the heteronuclear compounds [Cu 2 M(thd) 3 (OCH 2 CH 2 OCH 3 ) 3 ] (M = Ca, 6a ; M = Sr, 6b ). These heterometallic complexes were also obtained in the reaction of 1a and the mixed Ca and Sr complexes of β‐diketonate‐alkoxide [M x (thd) y (OCH 2 CH 2 OCH 3 ) 2x−y ] (M = Ca, x = 7, y = 6, 3 ; M = Sr, x = 5, y = 3, 4 ), respectively. In comparison, 1a reacts with the analogous [Ba(thd)(OCH 2 CH 2 OCH 3 )] ( 5a ) to yield a[Ba 2 Cu 2 (thd) 4 (OCH 3 ) 4 (HOCH 2 CH 2 OCH 3 ) 2 ] species ( 8a .) The in situ prepared mixed‐ligand Ba Compounds [Ba(thd)OR)] (R = CH 2 CH 2 OCH 2 CH 2 OCH 3 , ( 5b ); R = CH 2 CH 2 CH 2 OCH 3 ( 5c ) react with the corresponding Cu complexes [Cu(thd)(OR)] n (R = CH 2 CH 2 OCH 2 CH 2 OCH 3 ), n = 4 ( 1b ); R = CH 2 CH 2 OCH 2 CH 2 OCH 3 ( 8b ); R = CH 2 CH 2 CH 2 OCH 3 ( 8c ). However, [Cu(hfd)(OCH 2 CH 2 OCH 3 )] 4 (hfd = 1,1,1,5,5,5,‐hexafluoroacetylacetonate; 1e ) is converted in the presence of 2a–c to the simple metathesis products [M(hfd) 2 ] (M = Ca, Sr, Ba) and [Cu(OCH 2 CH 2 OCH 3 ) 2 ]. Crystalline [Ba 2 Cu 2 (hfd) 2 (thd) 2 (OCH 2 CH 2 CH 2 OCH 3 ) 4 (HOCH 2 CH 2 CH 2 OCH 3 ) 2 ] ( 9 ) was isolated from the reaction of 1a with in situ prepared [Ba((hfd)OCH 2 CH 2 CH 2 OCH 3 )] ( 5d ) in 2‐, methoxyethanol. X‐Ray crystallographic structure determinations are reported for 6a , 6b , 8b , and 8c .