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Reactivity of bis(organoamino)phosphanes with magnesium(II) compounds
Authors: Vrána Jan | Jambor Roman | Růžička Aleš | Alonso Mercedes | De Proft Frank | Lyčka Antonín | Dostál Libor
Year: 2015
Type of publication: článek v odborném periodiku
Name of source: Dalton Transactions
Publisher name: Royal Society of Chemistry
Place: Cambridge
Page from-to: 4533-4545
Titles:
Language Name Abstract Keywords
cze Reaktivita bis(organoamino)fosfánů s hořečnatými sloučeninami Byla studována reaktivita bis(organoamino)fosfánů PhP(NHR) [R = t-Bu (1), Ph (2)] a PhP(NEt2)(NHDip) (Dip = 2,6-i-Pr2C6H3)) s hořečnatými sloučeninami n-Bu2Mg a MeMgBr. Reaktivita; bisorganoaminofosfány; hořečnaté sloučeniny
eng Reactivity of bis(organoamino)phosphanes with magnesium(II) compounds 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)](2)Mg (5) depending on the stoichiometry. The treatment of 1 with MeMgBr led to the phosphinate [Ph(H)P(Nt-Bu)(2)](2)Mg (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)](2)Mg(THF)(2)}(2) (8), but the analogous reaction in a 2 : 1 molar ratio yielded phosphinate [Ph(H)P(NPh)(2)](2)Mg(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)](2)Mg (11) and {[PhP(NEt2)(NDip)(2)]Mg(mu-Br)(THF)}(2) (12), respectively. All products were characterized using H-1, C-13{H-1}and P-31 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. bond covalent radii; correlated molecular calculations; density-functional theory; gaussian-basis sets; x-ray structures; coordination chemistry; structural-characterization; theoretical investigations; polymerization catalysis; metal-complexes

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