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Issue 30, 2012
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Heterolytic addition of E–H bonds across Pt–P bonds in Pt N-heterocyclic phosphenium/phosphido complexes

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Abstract

The reactivity of E–H bonds (E = S, O, Cl) with Pt(II) complexes ligated by an N-heterocyclic phosphido-containing diphosphine ligand have been investigated. Addition of PhSH to [(PPP)Pt(PPh3)][PF6] (1) results in clean formation of [(PP(H)P)Pt(SPh)][PF6] (3), in which the substrate has added across the Pt–PNHP bond. Similar reactivity occurs when 1 is treated with ROH (R = Ph, Me), but in this case the O–H bond adds across the Pt–P bond in the opposite direction producing [(PP(OR)P)Pt(H)(PPh3)][PF6] (R = Ph (4), Me (5)). HCl addition to 1 cleanly generates [(PP(H)P)PtCl][PF6] (6PF6PF6PF6). The neutral Pt–NHP complex (PPP)PtCl (2) exhibits similar reactivity; however, in the presence of the nucleophilic Cl anion, the (PP(OR)P)Pt(H)Cl species presumably generated via addition of ROH (R = Me, Et) undergoes an Arbuzov-like dealkylation reaction to exclusively form the N-heterocylic phosphinito species (PP(O)P)Pt(H) (7).

Graphical abstract: Heterolytic addition of E–H bonds across Pt–P bonds in Pt N-heterocyclic phosphenium/phosphido complexes

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Publication details

The article was received on 24 Feb 2012, accepted on 16 Apr 2012 and first published on 11 May 2012


Article type: Paper
DOI: 10.1039/C2DT30455D
Citation: Dalton Trans., 2012,41, 9083-9090
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    Heterolytic addition of E–H bonds across Pt–P bonds in Pt N-heterocyclic phosphenium/phosphido complexes

    B. Pan, M. W. Bezpalko, B. M. Foxman and C. M. Thomas, Dalton Trans., 2012, 41, 9083
    DOI: 10.1039/C2DT30455D

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