Heteronuclear Alkoxide Compounds Containing Copper and Alkaline Earth Metals

Abstract

AbstractThe tetrameric Cu(β‐diketonate) alkoxide complex [Cu(thd)(OCH2CH2OCH3)]4 (thd = 2,2,6,6‐tetramethyl‐3,5‐heptanedionate; 1a) reacts with the alkaline earth metal alkoxides [M(OCH2CH2OCH3)2] (M = Ca, 2a; M = Sr, 2b; M = Ba, 2c) to yield the heteronuclear compounds [Cu2M(thd)3(OCH2CH2OCH3)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 [Mx(thd)y(OCH2CH2OCH3)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)(OCH2CH2OCH3)] (5a) to yield a[Ba2Cu2(thd)4(OCH3)4(HOCH2CH2OCH3)2] species (8a.) The in situ prepared mixed‐ligand Ba Compounds [Ba(thd)OR)] (R = CH2CH2OCH2CH2OCH3, (5b); R = CH2CH2CH2OCH3 (5c) react with the corresponding Cu complexes [Cu(thd)(OR)]n (R = CH2CH2OCH2CH2OCH3), n = 4 (1b); R = CH2CH2OCH2CH2OCH3 (8b); R = CH2CH2CH2OCH3 (8c). However, [Cu(hfd)(OCH2CH2OCH3)]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(OCH2CH2OCH3)2]. Crystalline [Ba2Cu2(hfd)2(thd)2(OCH2CH2CH2OCH3)4(HOCH2CH2CH2OCH3)2] (9) was isolated from the reaction of 1a with in situ prepared [Ba((hfd)OCH2CH2CH2OCH3)] (5d) in 2‐, methoxyethanol. X‐Ray crystallographic structure determinations are reported for 6a, 6b, 8b, and 8c.