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Article Dans Une Revue Dalton Transactions Année : 2014

Titanium imido complexes stabilised by bis(iminophosphoranyl)methanide ligands: the influence of N-substituents on solution dynamics and reactivity

Résumé

Terminal titanium imido complexes of the general formula [Ti(NtBu)Cl{CH(Ph2PNR)2}] 4 (R = Ph, iPr, tBu) are reported. These compounds were synthesized from the corresponding Li adducts 3 of BIPMH (bis(iminophosphoranyl)methanide) and Mountford's complex [Ti(NtBu)Cl2(Py)3]. The crystal structures of two of the Ti complexes (R = Ph, tBu) and two of the Li compounds (R = iPr, tBu) are reported. Dynamic solution NMR spectroscopy reveals a dynamic isomerisation process in the case of the Ti complex 4c (R = tBu). DFT studies showed that this dynamic process comes from steric repulsion between the imido ligand and the tBu N-substituents on the BIPMH ligand. Complexes 4 were tested in alkyne hydroamination; 4a (R = Ph) displayed modest catalytic activity in the reaction of aniline with phenylacetylene.
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Dates et versions

hal-02003810 , version 1 (07-12-2023)

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Adrien T. Normand, Alexandre Massard, Philippe Richard, Coline Canovas, Cédric Balan, et al.. Titanium imido complexes stabilised by bis(iminophosphoranyl)methanide ligands: the influence of N-substituents on solution dynamics and reactivity. Dalton Transactions, 2014, 43 (40), pp.15098-15110. ⟨10.1039/C4DT00746H⟩. ⟨hal-02003810⟩
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