Work

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

Year: 2014

Type: article

Abstract: 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.

Source: Dalton Transactions

DOI: 10.1039/c4dt00746h

Authors: Adrien T. Normand, Alexandre Massard, Philippe Richard, Coline Canovas, Cédric Balan, Michel Picquet, Audrey Auffrant, Pierre Le Gendre

Institutions: Centre National de la Recherche Scientifique, Université de Bourgogne, Institut de Chimie Moléculaire de l'Université de Bourgogne, École Polytechnique, Laboratoire de Chimie Moléculaire

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: Ministère de l'Enseignement Supérieur et de la Recherche, Centre National de la Recherche Scientifique, Conseil régional de Bourgogne-Franche-Comté

OpenAlex ID: W1997488343

FWCI: 0.29

Cites: 71

Cited by: 11

Related to: 10