Abstract

AbstractThe reaction of titanium isopropoxide, Ti(OiPr)4, with bis(trimethylsilyl) phosphonates has led to structures containingTi3O units [= Ti3(μ3‐O)(μ2‐OiPr)3(OiPr)3(O3PR)3] as the basic structural motif. This unit can be capped by a single Ti(OiPr)2L group (L = neutral ligand) through phosphonate bridges (for R = xylyl), or sandwich‐like structures can be formed with two Ti3O units bonded to a central Ti atom (for R = CH2CH2CH2Cl or benzyl). For R = allyl or ethyl, dimeric clusters were formed in which two Ti4 cluster units are bridged by isopropyl phosphonate ligands. For comparison, Ti(OiPr)4 was also treated with allylphosphonic acid to yield a Ti4 cluster. The reaction of Ti(OiPr)4 with the bulky bis(trimethylsilyl) 2‐naphthylmethyphosphonate did not yield an oxo cluster but instead the phosphonate‐substituted titanium alkoxide Ti4(OiPr)8(O3PCH2naphthyl)4.

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