The reactions of LAlH2 (L = HC(CMeNAr)2, Ar = 2,6-iPr2C6H3) (1) with diphenylsilanediol, phenylphosphonic acid, diphenylphosphinic acid, and pyrocatechol afford compounds with the Al–O–X (X = Si, P, C) motif of composition [LAl(μ-O)]2Si(Ph)2 (2), [LAl(μ-O)]2PO(Ph) (3), LAl[OPO(Ph)2]2 (4), and LAl(μ-O)2(o-C6H4) (5), respectively. Compound 2 contains the Al–O–Si–O–Al heterotrimetallic dioxide chain. Compound 3 features an Al(μ-O)]2P four-membered ring, while compound 4 exhibits a P–O–Al–O–P chain structure. Compound 5 contains the benzo-aluminum-dioxide organic–inorganic hybrid five-membered ring. Complexes 2, 3, 4, and 5 were characterized by NMR, elementary analysis, and single-crystal X-ray diffraction.
