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Issue 28, 2014
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Differences in the cyclometalation reactivity of bisphosphinimine-supported organo-rare earth complexes

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Abstract

The pyrrole-based ligand N,N′-((1H-pyrrole-2,5-diyl)bis(diphenylphosphoranylylidene))bis(4-isopropylaniline) (HLB) can be deprotonated and coordinated to yttrium and samarium ions upon reaction with their respective trialkyl precursors. In the case of yttrium, the resulting complex [LBY(CH2SiMe3)2] (1) is a Lewis base-free monomer that is remarkably resistant to cyclometalation. Conversely, the analogous samarium complex [LBSm(CH2SiMe3)2] is dramatically more reactive and undergoes rapid orthometalation of one phosphinimine aryl substituent, generating an unusual 4-membered azasamaracyclic THF adduct [κ4-LBSm(CH2SiMe3)(THF)2] (2). This species undergoes further transformation in solution to generate a new dinuclear species that features unique carbon and nitrogen bridging units [κ122-LBSm(THF)]2 (3). Alternatively, if 2 is intercepted by a second equivalent of HLB, the doubly-ligated samarium complex [(κ4-LB)LBSm] (4) forms.

Graphical abstract: Differences in the cyclometalation reactivity of bisphosphinimine-supported organo-rare earth complexes

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Article information


Submitted
22 Mar 2014
Accepted
02 May 2014
First published
15 May 2014

Dalton Trans., 2014,43, 10739-10750
Article type
Paper
Author version available

Differences in the cyclometalation reactivity of bisphosphinimine-supported organo-rare earth complexes

M. T. Zamora, K. R. D. Johnson, M. M. Hänninen and P. G. Hayes, Dalton Trans., 2014, 43, 10739
DOI: 10.1039/C4DT00863D

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