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Square-planar metal(II) complexes containing ester functionalised bis(phosphino) amines: Mild P-N methanolysis and C-arene-H cyclometallation
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dc.contributor.author | Gaw, Kirsty G. | |
dc.contributor.author | Smith, Martin B. | |
dc.contributor.author | Wright, John B. | |
dc.contributor.author | Slawin, Alexandra M. Z. | |
dc.contributor.author | Coles, Simon J. | |
dc.contributor.author | Hursthouse, Michael B. | |
dc.contributor.author | Tizzard, Graham J. | |
dc.date.accessioned | 2014-05-15T10:01:02Z | |
dc.date.available | 2014-05-15T10:01:02Z | |
dc.date.issued | 2012-02-15 | |
dc.identifier.citation | Gaw , K G , Smith , M B , Wright , J B , Slawin , A M Z , Coles , S J , Hursthouse , M B & Tizzard , G J 2012 , ' Square-planar metal(II) complexes containing ester functionalised bis(phosphino) amines: Mild P-N methanolysis and C-arene-H cyclometallation ' , Journal of Organometallic Chemistry , vol. 699 , pp. 39-47 . https://doi.org/10.1016/j.jorganchem.2011.11.003 | en |
dc.identifier.issn | 0022-328X | |
dc.identifier.other | PURE: 16867439 | |
dc.identifier.other | PURE UUID: 2b075db1-3d0a-4244-a459-91b74d299412 | |
dc.identifier.other | WOS: 000299118700007 | |
dc.identifier.other | Scopus: 84855682291 | |
dc.identifier.other | ORCID: /0000-0002-9527-6418/work/56862073 | |
dc.identifier.uri | https://hdl.handle.net/10023/4799 | |
dc.description | Funding: EPSRC studentship and Infinium UK Ltd | en |
dc.description.abstract | The synthesis of three new ester functionalised bis(phosphino)amines Ph2PN{R}PPh2 [R = C6H4(3-CO2Me) 1a; C6H3(3,5-CO2Me)(2) 1b; C6H4(4-CO2Me) 1c] upon stoichiometric reaction of Ph2PCl and the appropriate H2N{R} in Et2O is described. Reaction of 1 equiv. of 1a c with MCl2(cod) (M = Pt, Pd) in CH2Cl2 afforded the dichlorometal(II) complexes PtCl2(1a) 2a, PtCl2(1b) 2b, PtCl2(1c) 2c and PdCl2(1b) 2'b respectively. The corresponding dibromo (and diiodo) platinum(II) complexes 3b (and 4b) were synthesised, in > 80% isolated yields, from PtBr2(cod) or PtI2(cod). When a suspension of 2b in MeOH was stirred at r.t. for ca. 16 h the mixed complex cis-PtCl2[Ph2PNH{R}](Ph2POMe) 5a [R = C6H3(3,5-CO2Me)(2)] was cleanly generated. Metathesis of 5a using excess NaBr or NaI in MeOH/acetone afforded cisPtBr(2)[Ph2PNH{R}](Ph2POMe) 5b or cis-PtI2[Ph2PNH{R}](Ph2POMe) 5c. Methanolysis of PtCl2(1a) 2a at ambient temperature afforded, in low yield (18%), the regiospecific P, C-orthometallated complex cis-PtCl [Ph2PNH{C6H3(3-CO2Me)}](Ph2POMe) 6. We speculate the C - H activated complex 6 is obtained via initial formation of cis-PtCl2[Ph2PNH{C6H4(3-CO2Me)}](Ph2POMe) 7. A similar observation was also found using 2c whereupon examination of the isolated solid, by P-31{H-1} NMR spectroscopy, revealed formation of three complexes namely orthometallated cis-PtCl[Ph2PNH{C6H3(4-CO2Me)}](Ph2POMe) 9, cis-PtCl[Ph2PNH{C6H4(4-CO2Me)}](Ph2POMe) 10 and cis-PtCl2(Ph2POMe)(2) 8. All new compounds reported here have been characterised by multinuclear NMR and IR spectroscopy, microanalysis and in six cases by single crystal X-ray crystallography. The X-ray structure of cis-PtCl[Ph2PNH{C6H3(3-CO2Me)}]( Ph2POMe) 6 revealed selective C - H cycloplatination at the 6-position (as opposed to the 2-position) of the N-arene ring. | |
dc.format.extent | 9 | |
dc.language.iso | eng | |
dc.relation.ispartof | Journal of Organometallic Chemistry | en |
dc.rights | © The Authors. This is an open access article, available from http://www.sciencedirect.com | en |
dc.subject | Cyclometallation | en |
dc.subject | Metathesis | en |
dc.subject | Phosphine ligands | en |
dc.subject | Square-planar complexes | en |
dc.subject | X-ray crystallography | en |
dc.subject | Central carbene moiety | en |
dc.subject | Coordination chemistry | en |
dc.subject | Platinum(ii) complexes | en |
dc.subject | Substitution-reactions | en |
dc.subject | Palladium complexes | en |
dc.subject | Coupling reactions | en |
dc.subject | Iridium complexes | en |
dc.subject | Pincer complexes | en |
dc.subject | Phenyl ring | en |
dc.subject | Ligands | en |
dc.subject | QD Chemistry | en |
dc.subject.lcc | QD | en |
dc.title | Square-planar metal(II) complexes containing ester functionalised bis(phosphino) amines: Mild P-N methanolysis and C-arene-H cyclometallation | en |
dc.type | Journal article | en |
dc.description.version | Publisher PDF | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | https://doi.org/10.1016/j.jorganchem.2011.11.003 | |
dc.description.status | Peer reviewed | en |
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