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Alkali-metal- and alkaline-earth-metal-mediated C-O activation of an anisole-substituted phosphido-borane ligand

Lookup NU author(s): Dr Keith Izod, James Watson, Salima El-Hamruni, Dr Ross Harrington, Dr Paul Waddell



This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND).


© 2017 American Chemical Society. The reaction between {(Me3Si)2CH}PH(C6H4-2-OMe) (4) and 1 equiv of BH3·SMe2 yields the phosphine-borane {(Me3Si)2CH}PH(BH3)(C6H4-2-OMe) (5). Subsequent reaction between 5 and 1 equiv of n-BuLi in THF gives the phosphido-borane complex [{(Me3Si)2CH}P(BH3)(C6H4-2-OMe)]Li(THF) (6a), which was isolated as a colorless microcrystalline solid. Treatment of 5 with 1 equiv of PhCH2M yields the corresponding complexes [{(Me3Si)2CH}P(BH3)(C6H4-2-OMe)]ML (ML = Na(THF) (6b), K(pmdeta) (6c); pmdeta = N,N,N′,N″,N″-pentamethyldiethylenetriamine), after crystallization in the presence of the corresponding coligand. While compounds 6b,c are stable toward heat, compound 6a decomposes on heating to 50 °C in toluene to give the cluster [[{(Me3Si)2CH}PH(C6H4-2-O)]Li]6 (7) and the tertiary phosphine-borane {(Me3Si)2CH}P(BH3)(Me)(C6H4-2-OMe) (8). Related C-O cleavage reactions are observed when MgI2 is treated with 2 equiv of 6a and when CaI2 is treated with 2 equiv of [{(Me3Si)2CH}P(BH3)(C6H4-2-OMe)]K in THF, giving [{(Me3Si)2CH}P(BH3)(C6H4-2-O)Mg(THF)2]2 (9) and [{(Me3Si)2CH}P(BH3)(C6H4-2-O)Ca(THF)]4 (10), respectively, along with 1 equiv of 8 in each case. In contrast, the reaction between SrI2 and 2 equiv of [{(Me3Si)2CH}P(BH3)(C6H4-2-OMe)]K in THF yields [{(Me3Si)2CH}P(BH3)(C6H4-2-OMe)Sr(THF)4] (11).

Publication metadata

Author(s): Izod K, Watson JM, El-Hamruni SM, Harrington RW, Waddell PG

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2017

Volume: 36

Issue: 11

Pages: 2218-2227

Online publication date: 16/05/2017

Acceptance date: 02/04/2016

Date deposited: 04/07/2017

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society


DOI: 10.1021/acs.organomet.7b00262


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