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Complexes of platinum(II), platinum(IV), rhodium(III) and iridium(III) containing orthometallated triphenylphosphine

Bennett, Martin; Bhargava, Suresh; Ke, Mingzhe; Willis, Anthony

Description

Treatment of [PtCl2(SEt2)2] or [RhCl3(SEt2)3] with 2-LiC6H4PPh2 gives four-membered ring chelate arylplatinum(n) or arylrhodium(m) complexes [Pt{C6H4(PPh2)-2}3 and [Rh {C6H4(PPh2)-2}3], respectively, whereas the corresponding reaction of [IrCl3(SEt2)3] gives JrCl{C6H4(PPh2)-2}2(PPh 3)] arising from cleavage of an Ir-C6H4(PPh2) bond. The chemistry of [Pt{C6H4(PPh2)-2}2] is dominated by the lability of the Pt-P bonds, which are displaced sequentially by ligands at room temperature to give...[Show more]

dc.contributor.authorBennett, Martin
dc.contributor.authorBhargava, Suresh
dc.contributor.authorKe, Mingzhe
dc.contributor.authorWillis, Anthony
dc.date.accessioned2015-12-13T23:18:26Z
dc.date.available2015-12-13T23:18:26Z
dc.identifier.issn1477-9226
dc.identifier.urihttp://hdl.handle.net/1885/90178
dc.description.abstractTreatment of [PtCl2(SEt2)2] or [RhCl3(SEt2)3] with 2-LiC6H4PPh2 gives four-membered ring chelate arylplatinum(n) or arylrhodium(m) complexes [Pt{C6H4(PPh2)-2}3 and [Rh {C6H4(PPh2)-2}3], respectively, whereas the corresponding reaction of [IrCl3(SEt2)3] gives JrCl{C6H4(PPh2)-2}2(PPh 3)] arising from cleavage of an Ir-C6H4(PPh2) bond. The chemistry of [Pt{C6H4(PPh2)-2}2] is dominated by the lability of the Pt-P bonds, which are displaced sequentially by ligands at room temperature to give complexes containing monodentate C6H4(PPh2), i.e. [Pt{C6H4(PPh2)-2} {n-C6-H4(PPh2)-2}(L)] [L = PPh2, P(OPh)3, P(OMe)3 or Bu'NC] and [Pt{n'-C6H4(PPh2)-2}2(R 2PCH2CH2PR2)] (R = Ph, Me or Cy). In the cases of Me2PCH2CH2PMe2 and Cy2PCH2CH2PCy2, binuclear intermediates can be detected in which these ligands bridge two platinum atoms. Oxidative addition of methyl iodide or iodine to [Pt{C6H4(PPh2)-2}2] gives initially platinum(iv) complexes [PtI(R){C6H4(PPh2)-2}2] (R = Me or I) in which the added groups are mutually trans; in the final, stable products the added groups and the phosphorus atoms are, separately, mutually cis. Oxidative addition of bromine to [Pt{C6H4(PPh2)-2}2] gives initially trans-[PtBr2{C6H4(PPh2)-2} 2] but subsequent oxidation and hydrolysis at the phosphorus atoms gives chelate tertiary phosphine oxide complexes of platinum(iv). The molecular structures of [Rh{C6H4(PPh2)-2}3] and rö-[PtI(Me){C6H4(PPh2)-2}2] have been determined by X-ray crystallography.
dc.publisherRoyal Society of Chemistry
dc.sourceDalton Transactions
dc.titleComplexes of platinum(II), platinum(IV), rhodium(III) and iridium(III) containing orthometallated triphenylphosphine
dc.typeJournal article
local.description.notesImported from ARIES
local.description.refereedYes
dc.date.issued2000
local.identifier.absfor039904 - Organometallic Chemistry
local.identifier.ariespublicationMigratedxPub20471
local.type.statusPublished Version
local.contributor.affiliationBennett, Martin, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationBhargava, Suresh, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationKe, Mingzhe, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationWillis, Anthony, College of Physical and Mathematical Sciences, ANU
local.bibliographicCitation.startpage3537
local.bibliographicCitation.lastpage3545
local.identifier.doi10.1039/b004908p
dc.date.updated2015-12-12T08:56:46Z
local.identifier.scopusID2-s2.0-0001872124
CollectionsANU Research Publications

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