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Issue 31, 2012
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Rearrangements of phosphinoimines to phosphine–imines in ruthenium chelate complexes

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Abstract

Thermal reaction of 1 : 1 mixtures of the RuCl2(PPh3)3 and phosphinoimine R2PN[double bond, length as m-dash]CPh2 (R = Ph, iPr, Me) at 140 °C results in isolation of the dimeric species [RuCl(μ-Cl)(PPh3)(C6H4(PPh2)C(Ph)NH)]2 (R = Ph 1, iPr 2, Me 3) containing phosphine–imine chelating ligands. Subsequent reaction of 1 and 3 with one equivalent of pyridine at room temperature give RuCl2(PPh3)(py)(C6H4(PR2)C(Ph)NH) (R = Ph 4, Me 5). Excess pyridine reacts with 2 to give a mixture of the cis and trans-isomers of RuCl2(py)2(C6H4(PiPr2)C(Ph)NH) 6 and 7 respectively. Treatment of 5 with excess PPh3 affords RuCl2(PPh3)2(C6H4(PMe2)C(Ph)NH) 8. Aspects of the mechanism of the thermal rearrangements of the phosphinoimine to the phosphineimine ligands are considered and the isolation of RuCl2(Ph2PN[double bond, length as m-dash]CPh2)(SIMes)(CHPh) 9 and RuCl2(PPh3)2(HN[double bond, length as m-dash]C(Ph)C6H4) 10 provide support for a proposed mechanism involving a intermediate containing a Ru-bound metallated aryl-imine fragment.

Graphical abstract: Rearrangements of phosphinoimines to phosphine–imines in ruthenium chelate complexes

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Publication details

The article was received on 02 Mar 2012, accepted on 12 Jun 2012 and first published on 27 Jun 2012


Article type: Paper
DOI: 10.1039/C2DT30505D
Citation: Dalton Trans., 2012,41, 9431-9438
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    Rearrangements of phosphinoimines to phosphine–imines in ruthenium chelate complexes

    C. C. Brown and D. W. Stephan, Dalton Trans., 2012, 41, 9431
    DOI: 10.1039/C2DT30505D

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