6533b823fe1ef96bd127e189
RESEARCH PRODUCT
Titanium imido complexes stabilised by bis(iminophosphoranyl)methanide ligands: the influence of N-substituents on solution dynamics and reactivity
Alexandre MassardCédric BalanMichel PicquetColine CanovasPierre Le GendreAudrey AuffrantAdrien T. NormandPhilippe Richardsubject
chemistry.chemical_classificationLigandAlkyneNuclear magnetic resonance spectroscopyCrystal structurePhotochemistryMedicinal chemistryAdductInorganic Chemistrychemistry.chemical_compoundchemistryPhenylacetyleneReactivity (chemistry)Hydroamination[CHIM.OTHE]Chemical Sciences/OtherComputingMilieux_MISCELLANEOUSdescription
Terminal titanium imido complexes of the general formula [Ti(N(t)Bu)Cl{CH(Ph2PNR)2}] 4 (R = Ph, (i)Pr, (t)Bu) are reported. These compounds were synthesized from the corresponding Li adducts 3 of BIPMH (bis(iminophosphoranyl)methanide) and Mountford's complex [Ti(N(t)Bu)Cl2(Py)3]. The crystal structures of two of the Ti complexes (R = Ph, (t)Bu) and two of the Li compounds (R = (i)Pr, (t)Bu) are reported. Dynamic solution NMR spectroscopy reveals a dynamic isomerisation process in the case of the Ti complex 4c (R = (t)Bu). DFT studies showed that this dynamic process comes from steric repulsion between the imido ligand and the (t)Bu 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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2014-10-28 |