2006
DOI: 10.1021/ic061201s
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Mononucleating Bis(β-diketonate) Ligands and Their Titanium(IV) Complexes

Abstract: Novel bis(beta-diketones) linked by 2,2'-biphenyldiyl, 2,2'-tolandiyl, and 2,2'-bis(methylene)biphenyl moieties have been prepared. All are metalated readily by titanium(IV) isopropoxide, but the nature of the complexes formed depends on the linker structure. The biphenyl-bridged ligand gives only traces of a mononuclear complex, which is thermodynamically unstable with respect to oligomerization. The tolan-bridged ligand does form mononuclear complexes, but only as a mixture of geometric isomers. In contrast,… Show more

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Cited by 12 publications
(25 citation statements)
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“…17 The equatorial Ti-O bonds trans to triflate are the shortest known in (dike) 2 Ti compounds, shorter even than the 1.944 Å bond trans to ether in the cationic etherate [(Tol 2 Bob)Ti(O i Pr)(OEt 2 )]BAr F . 5 The titanium-triflate distances are typical of those seen in other titanium triflates in oxygen-rich environments. 18 If a slightly deficient amount of HOTf is used and the product precipitated promptly with hexane, then optically pure (S,D)-(Tol 2 Bob)Ti(OTf) 2 can be prepared from the binaphtholate complex (eqn (3)), although the triflate is contaminated by traces (~2%) of the binaphtholate.…”
Section: Resolution Of the (Tol 2 Bob)ti Fragment Through Formation O...mentioning
confidence: 81%
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“…17 The equatorial Ti-O bonds trans to triflate are the shortest known in (dike) 2 Ti compounds, shorter even than the 1.944 Å bond trans to ether in the cationic etherate [(Tol 2 Bob)Ti(O i Pr)(OEt 2 )]BAr F . 5 The titanium-triflate distances are typical of those seen in other titanium triflates in oxygen-rich environments. 18 If a slightly deficient amount of HOTf is used and the product precipitated promptly with hexane, then optically pure (S,D)-(Tol 2 Bob)Ti(OTf) 2 can be prepared from the binaphtholate complex (eqn (3)), although the triflate is contaminated by traces (~2%) of the binaphtholate.…”
Section: Resolution Of the (Tol 2 Bob)ti Fragment Through Formation O...mentioning
confidence: 81%
“…Analogous metalation of the biphenyl-bridged Tol 2 BobH 2 ligand at room temperature produces a mixture of monomeric and oligomeric compounds, which require heating in the presence of excess Ti(O i Pr) 4 to convert to the desired monomer. 5 In contrast, the binaphthyl-bridged compound gives only monomeric product (as judged by in situ 1 H NMR spectroscopy), so metalation can be carried out at room temperature and without excess titanium. The 1 H NMR spectrum of (Tol 2 Bobbinap)Ti(O i Pr) 2 is very similar to that of its biphenyl-bridged analogue, except that one of the diastereotopic methylene protons and the diketonate methine proton are shifted markedly upfield in the binaphthyl Scheme 2 Preparation and reactivity of (R,K)-(Tol 2 Bobbinap)Ti(O i Pr) 2 .…”
Section: Optically Active Complexes Of Bis(methylene)binaphthyl Bridg...mentioning
confidence: 99%
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“…6 Ugrinova et al employed bis(b-diketones) linked by 2,2¢-biphenyldiyl, 2,2¢tolandiyl or 2,2¢-bis(methylene)biphenyl moieties in the reaction with Ti(OiPr) 4 and obtained monomeric complexes Ti(OR) 2 [bis(bdiketonate)]. 7 The special linkers favoured coordination of both b-diketonate units to the same metal. As a matter of fact, bis(bdiketonates) are known to form various cyclic structures with late transition metal ions (e.g.…”
Section: Introductionmentioning
confidence: 99%
“…The dark purple dichloride complex An2N LTiCl 2 can be prepared by reaction of the corresponding diisopropoxide complex with Me 3 SiCl (eqn (3)), a procedure which has also been used to prepare bis(diketonato)titanium(IV) dichlorides. 9, 27 The monochloro complex An2N LTi(O i Pr)Cl can be observed as an intermediate in this reaction by in situ NMR monitoring. NMR resonances for the isolated dichloride complex are broadened due to partial oxidation of the triarylamine groups.…”
Section: Synthesis and Structures Of Titanium(iv) Salan Complexesmentioning
confidence: 98%