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Access to Alkynylpalladium(IV) and -Platinum(IV) Species, Including Triorgano(diphosphine)metal(IV) Complexes and the Structural Study of an Alkynyl(pincer)platinum(IV) Complex, Pt(O2CArF)I(CCSiMe3)(NCN) (ArF = 4-CF3C6H4, NCN = [2,6-(dimethylaminomethyl)phenyl-N,C,N]-)

Citation

Canty, AJ and Rodemann, T and Skelton, BW and White, AH, Access to Alkynylpalladium(IV) and -Platinum(IV) Species, Including Triorgano(diphosphine)metal(IV) Complexes and the Structural Study of an Alkynyl(pincer)platinum(IV) Complex, Pt(O2CArF)I(CCSiMe3)(NCN) (ArF = 4-CF3C6H4, NCN = [2,6-(dimethylaminomethyl)phenyl-N,C,N]-), Organometallics, 25, (16) pp. 3996-4001. ISSN 0276-7333 (2006) [Refereed Article]

DOI: doi:10.1021/om0601495

Abstract

New classes of alkynylplatinum(IV) complexes are described, and the first examples of alkynylpalladium(IV) complexes have been detected, including a triorganopalladium(IV) diphosphine complex. Alkynyliodine(III) triflate reagents IPh(C≡CR2)(OTf) (R2 = SiMe3, Ph) are able to transfer alkynyl groups to diorganoplatinum(II) and "pincer" complexes Pt(O2CAr)(NCN) (NCN = [2,6-(dimethylaminomethyl)-phenyl-N, C,N]-, Ar = Ph, 4-trifluoromethylphenyl (ArF)); on addition of iodide ion, complexes with new alkynylplatinum(IV) kernels may be isolated: PtIMe2(C≡CR2)(bpy) (1, 2, 3a) (bpy = 2,2′-bipyridine), PtI(C4H8)(C≡CSiMe 3)(bpy) (4a), PtIPh2(C≡CSiMe3)(Bu 2 tbpy) (5a), and PtI(O2CAr)(C≡CR 2)(NCN) [Ar = Ph (14, 15), ArF (16, 17)]. For the reagent PtMe2(dmpe) [dmpe = 1,2-bis(dimethylphosphino)ethane], the unstable complexes PtIMe2(C≡CR2)(dmpe) (6a, 8a) are detected prior to reductive elimination of ethane and isolation of PtI(C≡CR 2)(dmpe) (7, 9). Isomerism is exhibited by the octahedral fac-Pt IVR2-(C≡CR2) complexes, where complexes 1 and 2 form as a mixture of complexes with the alkynyl group opposite the bidentate ligand and cis to the iodo ligand (1a-6a, 8a), and cis to the bidentate ligand and trans to the iodo ligand (1b, 2b), complexes 3a-5a, 6a, and 8a having R groups mutually cis. An X-ray structural analysis for 16 shows distorted octahedral geometry about the metal with the iodo ligand trans to the carbon donor of the mer-pincer ligand. Studies of the reactivity of related palladium(II) substrates at low temperature allow detection of the pincer complex Pd(O2CPh)(OTf)(C≡CSiMe3)(NCN) (19) and PdIMe2(C≡CSiMe3)(dmpe) (18) as a model for frequently proposed "PdIVXR3P2" species in catalytic and stoichiometric reactions. © 2006 American Chemical Society.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Canty, AJ (Professor Allan Canty)
Author:Rodemann, T (Dr Thomas Rodemann)
ID Code:43312
Year Published:2006
Web of Science® Times Cited:54
Deposited By:Chemistry
Deposited On:2006-08-01
Last Modified:2007-10-12
Downloads:0

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