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Issue 40, 2014
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Titanium imido complexes stabilised by bis(iminophosphoranyl)methanide ligands: the influence of N-substituents on solution dynamics and reactivity

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Abstract

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.

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

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Publication details

The article was received on 12 Mar 2014, accepted on 11 Apr 2014 and first published on 13 May 2014


Article type: Paper
DOI: 10.1039/C4DT00746H
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Dalton Trans., 2014,43, 15098-15110

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

    A. T. Normand, A. Massard, P. Richard, C. Canovas, C. Balan, M. Picquet, A. Auffrant and P. Le Gendre, Dalton Trans., 2014, 43, 15098
    DOI: 10.1039/C4DT00746H

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