Issue 10, 2015

Reactivity of bis(organoamino)phosphanes with magnesium(ii) compounds

Abstract

The reactivity of three phosphanes (PhP(NHR)2 [R = t-Bu (1), Ph (2)] and PhP(NEt2)(NHDip) (3) (where Dip = 2,6-i-Pr2C6H3)) with n-Bu2Mg and MeMgBr is presented. In the case of 1, the reaction with n-Bu2Mg gave [PhP(NHt-Bu)(Nt-Bu)]Mg(n-Bu) (4) or [PhP(NHt-Bu)(Nt-Bu)]2Mg (5) depending on the stoichiometry. The treatment of 1 with MeMgBr led to the phosphinate [Ph(H)P(Nt-Bu)2]2Mg (7) as a result of both the NH→PH tautomeric transformation and elimination of MgBr2 from the non-isolable intermediate [PhP(NHt-Bu)(Nt-Bu)]MgBr(THF) (6). Phosphane 2 reacted with n-Bu2Mg in a 1 : 1 molar ratio resulting in the formation of {[PhP(NPh)2]2Mg(THF)2}2 (8), but the analogous reaction in a 2 : 1 molar ratio yielded phosphinate [Ph(H)P(NPh)2]2Mg(THF) (9). The heteroleptic compound [Ph(H)P(NPh)2]MgBr(THF)2 (10) was obtained by the reaction of 2 with MeMgBr. Finally, the reaction of 3 with n-Bu2Mg and MeMgBr produced compounds [PhP(NEt2)(NDip)]2Mg (11) and {[PhP(NEt2)(NDip)2]Mg(μ-Br)(THF)}2 (12), respectively. All products were characterized using 1H, 13C{1H} and 31P NMR spectroscopy and, except for compounds 4 and 6, their molecular structures were determined using single-crystal X-ray diffraction analysis. In addition, a theoretical study on plausible isomers of 10 was performed to provide additional evidence for the presence of a syn- and anti-isomer in dynamic equilibrium in a solution of 10.

Graphical abstract: Reactivity of bis(organoamino)phosphanes with magnesium(ii) compounds

Supplementary files

Article information

Article type
Paper
Submitted
19 Dec 2014
Accepted
16 Jan 2015
First published
16 Jan 2015

Dalton Trans., 2015,44, 4533-4545

Author version available

Reactivity of bis(organoamino)phosphanes with magnesium(II) compounds

J. Vrána, R. Jambor, A. Růžička, M. Alonso, F. De Proft, A. Lyčka and L. Dostál, Dalton Trans., 2015, 44, 4533 DOI: 10.1039/C4DT03929G

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