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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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Allan J. Canty,*^† Melanie C. Denney,^† Gerard van Koten,*^‡ Brian W. Skelton,^§ and Allan H. White^§

School of Chemistry, University of Tasmania, Hobart, Tasmania, 7001 Australia, Debye Institute, Department of Metal-Mediated Synthesis, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands, and School of Biomedical and Chemical Sciences, University of Western Australia, Crawley, Western Australia 6009, Australia

Organometallics, 2004, 23 (23), pp 5432–5439

DOI: 10.1021/om040061w

Publication Date (Web): October 7, 2004

Section:

Organometallic and Organometalloidal Compounds

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 Pt^IV-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 Pt^IVMe analogue 7, the Pt^IVTol 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.

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Published In Issue November 08, 2004
Received April 28, 2004

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Article

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

Abstract

Citing Articles

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The 2-Indenylidene Chloropalladate {PdCl[Ind(Ph₂P═S)₂]}(nBu₄N): A Versatile Pincer Complex with “Innocent” and “Noninnocent” Behavior

One-Pot Synthesis of Symmetrical and Unsymmetrical Aryl Sulfides by Pd-Catalyzed Couplings of Aryl Halides and Thioacetates

One-Pot Synthesis of Symmetrical and Unsymmetrical Aryl Sulfides by Pd-Catalyzed Couplings of Aryl Halides and Thioacetates

Thermal C−H Bond Activation of Benzene, Toluene, and Methane with Cationic [M(X)(bipy)]⁺ (M = Ni, Pd, Pt; X = CH₃, Cl; bipy = 2,2′-bipyridine): A Mechanistic Study

Thermal C−H Bond Activation of Benzene, Toluene, and Methane with Cationic [M(X)(bipy)]⁺ (M = Ni, Pd, Pt; X = CH₃, Cl; bipy = 2,2′-bipyridine): A Mechanistic Study

Catalysis by Palladium Pincer Complexes

Catalysis by Palladium Pincer Complexes

Stable Mononuclear Organometallic Pd(III) Complexes and Their C−C Bond Formation Reactivity