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Arene coordination to yttrium(III) via carbon-carbon bond formation

journal contribution
posted on 2023-06-07, 20:20 authored by Michael D Fryzuk, Laleh Jafarpour, Francesca M Kerton, Jason Love, Brian O Patrick, Steven J Rettig
The synthesis and characterization of a series of yttrium and lanthanide complexes that incorporate the macrocyclic bis(amidophosphine) ligand PhP(CH2SiMe2NSiMe2CH2)2PPh, [P2N2], are described. The starting materials, {[P2N2]M}2(µ-Cl)2, (M = Y, Sm, Ho, Yb, Lu), are prepared by the reaction of syn-Li2(dioxane)[P2N2] with MCl3(THF)3 in toluene. The reactivity of these complexes toward PhLi and other arylating agents is dependent on the size of the M3+ ion. M = Y and Ho undergo C-C bond formation reactions to give biphenyldiide compounds {[P2N2]M}2{µ-?6:?6‘-(C6H5)2} and {[P2N2]Y}2{µ-?6:?6‘-(C6H4-p-Ph)2}. These have been structurally characterized and show the biphenyl dianion bridging two [P2N2]M fragments. These [P2N2]M fragments migrate over the bridging ligand's p-surface on the NMR time scale. M = Yb yields the paramagnetic monophenyl derivative [P2N2]Yb(C6H5), where the Yb center is coordinatively unsaturated and resides in a distorted square-pyramidal environment. M = Lu results in a mixture of “ate” complexes of the formulation “[P2N2]LuPLiCl”, as evidenced by 7Li NMR. However, the biphenyl product {[P2N2]Lu}2{µ-?6:?6‘-(C6H5)2} can be synthesized via a reductive route. The presence of THF was found to be deleterious to the coupling reaction; in this case, the THF adduct [P2N2]Y(C6H4-p-Me)(THF) was isolated and structurally characterized. The mechanism for the C-C bond formation reaction is described based on the isolation of these yttrium and lanthanide complexes.

History

Publication status

  • Published

Journal

Journal of the American Chemical Society

ISSN

0002-7863

Publisher

American Chemical Society

Issue

38

Volume

119

Page range

9071 - 9072

ISBN

0002-7863

Department affiliated with

  • Chemistry Publications

Full text available

  • No

Peer reviewed?

  • Yes

Legacy Posted Date

2012-02-06

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