Substituent effects in the formation of aryloxide-bridged europium complexes

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Abstract
The reactivity of europium in liquid ammonia with 2,6-disubstituted phenols has been surveyed and the effect of the 2,6 substituents on the bridging ability of the aryloxides has been examined. Monomeric and tetrameric complexes of Eu II have been isolated with tert-butyl and isopropyl substituents, Eu(OC 6 H 3 Bu t 2 -2,6) 2 (NCMe) 4 1 and Eu 4 (µ-OC 6 H 3 Pr i 2 -2,6) 4 (OC 6 H 3 Pr i 2 -2,6) 2 (µ 3 -OH) 2 (NCMe) 6 2, respectively, which can be compared to the previously reported bimetallic complex, (dme) 2 Eu(µ-OC 6 H 3 Me 2 -2,6) 3 Eu(OC 6 H 3 Me 2 - 2,6)(dme) 3, isolated with methyl substituents (dme = 1,2-dimethoxyethane). Acetonitrile has been found to be an excellent solvating ligand for the formation of crystalline complexes in this series. Complex 1 crystallizes from acetonitrile in the monoclinic space group P2 1 /c with a = 11.7117(14), b = 17.616(2), c = 18.263(2) Å, β = 91.318(8)°, U = 3766.8(7) Å 3 and D c = 1.282 Mg m -3 for Z = 4. Complex 2 crystallizes from acetonitrile in the monoclinic space group P2 1 /n with a = 13.676(3), b = 20.325(4), c = 32.632(6) Å, β = 91.068(12)°, U = 9069(3) Å 3 and D c = 1.429 Mg m -3 for Z = 4.

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