Due to routine maintenance, access to the Library Open Repository will be interrupted on the morning of Friday 12th February.
We apologise for any inconvenience.

Library Open Repository

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]-)

Downloads

Downloads per month over past year

Canty, AJ and Rodemann, T and Skelton, BW and White, AH (2006) 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. pp. 3996-4001.

[img] PDF
om0601495.pdf | Request a copy
Full text restricted
Available under University of Tasmania Standard License.

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(CCR²)(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(CCR²)(bpy) (1, 2, 3a) (bpy) 2,2`-bipyridine), PtI(C4H8)(CCSiMe3)(bpy)(4a), PtIPh2(CCSiMe3)(But2 bpy)(5a), and PtI(O2CAr)(CCR)(NCN) [Ar = Ph (14, 15), ArF (16, 17)]. For the reagent PtMe2(dmpe) [dmpe = 1,2-bis(dimethylphosphino)ethane], the unstable complexes PtIMe2(CCR²)(dmpe)(6a, 8a) are detected prior to reductive elimination of ethane and isolation of PtI(C=CR²)(dmpe) (7, 9). Isomerism is exhibited by the octahedral fac-PtIVR2(CCR2) 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)(CCSiMe3)(NCN)(19) and PdIMe2(CCSiMe3)(dmpe)(18) as a model for frequently proposed “PdIVXR3P2” species in catalytic and stoichiometric reactions.

Item Type: Article
Keywords: palladium, platinum, organopalladium, organoplatinum, pincer, alkynyl, palladium(IV), iodonium
Journal or Publication Title: Organometallics
Page Range: pp. 3996-4001
Identification Number - DOI: 10.1021/om0601495
Date Deposited: 26 Sep 2007
Last Modified: 18 Nov 2014 03:22
Item Statistics: View statistics for this item

Repository Staff Only (login required)

Item Control Page Item Control Page