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Carbon-Oxygen bond formation at Metal(IV) Centers: Reactivity of Palladium(II) and Platinum(II) Complexes of the [2,6-(Dimethylaminomethyl)phenyl-N,C,N]- (Pincer) Ligand toward Iodomethane and Dibenzoyl Peroxide; Structural Studies of M(II) and M(IV) Complexes

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Canty, AJ, Denney, MC, van Koten, G, Skelton, BW and White, AH 2004 , 'Carbon-Oxygen bond formation at Metal(IV) Centers: Reactivity of Palladium(II) and Platinum(II) Complexes of the [2,6-(Dimethylaminomethyl)phenyl-N,C,N]- (Pincer) Ligand toward Iodomethane and Dibenzoyl Peroxide; Structural Studies of M(II) and M(IV) Complexes' , Organometallics, vol. 23 , pp. 5432-5439 , doi: 10.1021/om040061w.

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Abstract

The presence of the [2,6-(dimethylaminomethyl)phenyl-N,C,N]- (pincer) ligand (NCN) in
platinum(II) complexes has been used to generate stable organoplatinum(IV) complexes that
model possible intermediates and reactivity in metal-catalyzed C-O bond formation
processes. The complexes M(O2CPh)(NCN) [M ) Pd (1), Pt (2)] were obtained by metathesis
reactions from the chloro analogues, and although 1 does not react with dibenzoyl peroxide,
2 does so to form Pt(O2CPh)3(NCN) (3) as a model intermediate for the acetoxylation of
arenes by acetic acid in the presence of palladium(II) acetate and an oxidizing agent. The
complex Pt(O2CPh)(NCN) (2) reacts with iodomethane in a complex manner to form PtI-
(NCN) (6) and cis-Pt(O2CPh)2Me(NCN) (7). Complex 7 decomposes to form Pt(O2CPh)(NCN)
(2) and MeO2CPh, probably via benzoate dissociation followed by nucleophilic attack by the
benzoate ion at the PtIV-Me carbon atom. The Pd(II) analogue Pd(O2CPh)(NCN) (1) reacts
with MeI to give PdI(NCN) (8) and MeO2CPh, for which the potential intermediacy of Pd-
(IV) species could not confirmed by 1H NMR spectroscopy. The complex PtTol(NCN) (4) (Tol
) 4-tolyl) reacts with (PhCO2)2 to form cis-Pt(O2CPh)2Tol(NCN) (5), but, unlike the PtIVMe
analogue 7, the PtIVTol complex 5 does not undergo facile C-O bond formation. X-ray
structural studies of the isostructural square-planar complexes M(O2CPh)(NCN) (1, 2) and
of the octahedral Pt(IV) complexes as solvates 3.1/2Me2CO, 5.Me2CO, and 7.Me2CO.H2O are reported. Complexes 5 and 7 have cis-PtC2 and cis-Pt(O2CPh)2 configurations.

Item Type: Article
Authors/Creators:Canty, AJ and Denney, MC and van Koten, G and Skelton, BW and White, AH
Keywords: organopalladium, organoplatinum, palladium(IV), iodonium, oxidative addition, pincer, intramolecular coordination
Journal or Publication Title: Organometallics
DOI / ID Number: 10.1021/om040061w
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