2013
DOI: 10.1002/ejic.201300859
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Influence of the Phosphonate Ligand on the Structure of Phosphonate‐Substituted Titanium Oxo Clusters

Abstract: The 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 clu… Show more

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Cited by 35 publications
(34 citation statements)
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“…In contrast to the previously obtained clusters with symmetrical, phosphonate‐substituted Ti 3 (μ 3 ‐O)(μ 2 ‐O i Pr) 3 (O i Pr) 3 units as the basic structural motif,4,5 the structure of 1 is based on unsymmetrically substituted Ti 3 (μ 3 ‐O)(μ 2 ‐O i Pr) 2 (O i Pr) 3 (μ 2 ‐OAc) units. Two Ti atoms (Ti1 and Ti2) of this unit are bridged by both an O i Pr and an acetate ligand, whereas Ti1 and Ti3 are singly bridged by a μ 2 ‐O i Pr group.…”
Section: Resultscontrasting
confidence: 67%
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“…In contrast to the previously obtained clusters with symmetrical, phosphonate‐substituted Ti 3 (μ 3 ‐O)(μ 2 ‐O i Pr) 3 (O i Pr) 3 units as the basic structural motif,4,5 the structure of 1 is based on unsymmetrically substituted Ti 3 (μ 3 ‐O)(μ 2 ‐O i Pr) 2 (O i Pr) 3 (μ 2 ‐OAc) units. Two Ti atoms (Ti1 and Ti2) of this unit are bridged by both an O i Pr and an acetate ligand, whereas Ti1 and Ti3 are singly bridged by a μ 2 ‐O i Pr group.…”
Section: Resultscontrasting
confidence: 67%
“…In contrast to reactions of Ti(O i Pr) 4 with bis(trimethylsilyl) phosphonates in the absence of acetic acid,5 a series of isostructural clusters [Ti 6 O 4 (O i Pr) 10 (OAc) 2 (O 3 PR) 2 ] was obtained both with much bulkier groups at the phosphorus atom, such as R = CH 2 –naphthyl ( 2 ), and with functional organic groups, such as R = vinyl ( 3 ), allyl ( 4 ), or CH 2 CH 2 CH 2 Cl ( 5 ) [Equation (1)]. This cluster type therefore appears to be rather robust.…”
Section: Resultsmentioning
confidence: 99%
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“…37,38 Most titanium phosphonates reported in the literature so far were synthesized under basic conditions (<1 equivalent of phosphonic acid). [39][40][41] In a previous publication we thoroughly investigated the solution stability of two titanium oxo-alkoxides modied with phenylphosphonate ligands using multiple NMR techniques. 42 In this work we synthesized a series of titanium (oxo-) alkoxides modied with tert-butylphosphonic acid, using 0.85, 1, 2 and 4 equivalents of phosphonic acid, to obtain formally basic, neutral and acidic reaction conditions.…”
Section: Introductionmentioning
confidence: 99%