Heterobi- and trimetallic cerium(IV) tert-butoxides with mono-, di-, and trivalent metals (M = K(I), Ge(II), Sn(II), Pb(II), Al(III), Fe(III)).

The reaction of Cerium Ammonium Nitrate (CAN) with varying amounts of KOtBu produced homometallic Ce(OtBu)4(NC5H5)2 (1) and the heterometallic derivative KCe2(OtBu)10 (3) characterized by X-ray diffraction and NMR spectroscopy. The oxo-alkoxide cluster Ce3O(OtBu)9 (2) was obtained from a solution of cerium(IV) tetrakis(tert-butoxide) in n-heptane under stringent precautions to avoid any adventitious hydrolysis. Lewis acid-base reactions of in situ generated Ce(OtBu)4(THF)2 (THF = tetrahydrofuran) with bi- and trivalent metal alkoxides [M(OtBu)x]n (M = Ge, Sn; x = 2; n = 2; M = Pb, x = 2; n = 3; M = Al, Fe; x = 3; n = 2) resulted in volatile products of the general formula MCe(OtBu)4+x (M = Al (4), Fe (5); x = 3; M = Ge (8), Sn (9), Pb (10); x = 2) in high yields. By dissolving 4 and 5 in pyridine the solvent adducts MCe(OtBu)7(NC5H5) (M = Al (6), Fe (7)) were formed, whereas 8 and 9 reacted with Mo(CO)6 in boiling toluene to yield the termetallic complexes (CO)5MoM(μ2-OtBu)3Ce(OtBu)3 (M = Ge (11), Sn (12)...