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Germylenes and stannylenes stabilized within N2PE rings (E = Ge or Sn): combined experimental and theoretical study
Authors: Vrána Jan | Ketkov Sergey | Jambor Roman | Růžička Aleš | Lyčka Antonín | Dostál Libor
Year: 2016
Type of publication: článek v odborném periodiku
Name of source: Dalton Transactions
Publisher name: Royal Society of Chemistry
Place: Cambridge
Page from-to: 10343-10354
Titles:
Language Name Abstract Keywords
cze Germyleny a stannyleny stabilizované N2PE kruhy Byla studována reaktivita aminophosphanu PhP(NHR)(2) (R = t-Bu a Dip; Dip = 2,6-i-Pr2C6H3) a t-BuP (NHDip) (2) a n-BuLi za vzniku sloučenin {[PhP(Nt-Bu) (2)]Li-2}(2) (1), [PhP(Nt-Bu)(NDip)]Li-2 (3), [t-BuP(NDip)(2)]Li-2 (5) a [t-BuP(NDip)(2)]Li-2. Germyleny; stannyleny; stabilizované; N2PE; kruhy
eng Germylenes and stannylenes stabilized within N2PE rings (E = Ge or Sn): combined experimental and theoretical study The deprotonation of aminophosphanes PhP(NHR)(2) (R = t-Bu or Dip; Dip = 2,6-i-Pr2C6H3) and t-BuP (NHDip)(2) using n-BuLi gave, depending on the stoichiometry, both the dilithium compounds {[PhP(Nt-Bu) (2)]Li-2}(2) (1), [PhP(Nt-Bu)(NDip)]Li-2 center dot(Et2O) (3), [t-BuP(NDip)(2)]Li-2 center dot(Et2O)(2) (5) and [t-BuP(NDip)(2)]Li-2 center dot(tmeda)(2) (5a), and the monolithium compounds [PhP(NHt-Bu)(NR)]Li center dot(tmeda) (R = t-Bu 2, Dip 4) and [t-BuP (NHDip)(NDip)]Li center dot(tmeda) (6). Treatment of 1, 3 and 5 with GeCl2 center dot dioxane or SnCl2 in a 1 : 1 stoichiometric ratio gave the corresponding tetrylenes [PhP(Nt-Bu)(2)] E (E = Ge 7, Sn 10), [PhP(Nt-Bu)(NDip)] Ge (8) and [t-BuP(NDip)(2)] E (E = Ge 9, Sn 11). The heteroleptic germylene [Ph(H)P(Nt-Bu)(2)] GeCl (12) was obtained by the reaction of the monolithium compound [PhP(NHt-Bu)(Nt-Bu)]Li center dot(tmeda) (2) with GeCl2 center dot dioxane in a 1 : 1 stoichiometric ratio, as a result of a spontaneous NH -> PH tautomeric shift in the ligand backbone. In contrast, an analogous reaction with SnCl2 produced only stannylene 10 along with the PhP(NHt-Bu)(2) starting material, suggesting scrambling of the ligands rather than a NH -> PH tautomeric shift. Finally, heating 5a in solution led to P-C bond cleavage and formation of the bis(imino) phosphide [DipNPNDip] Li center dot(tmeda) (13). The reaction of 13 with GeCl2 center dot dioxane, SnCl2 or PbCl2 in a 2 : 1 stoichiometric ratio yielded the unprecedented tetrylenes [DipNPNDip](2)E (E = Ge 14, Sn 15 and Pb 16), in which the tetrylene center is incorporated within two N2PE rings. Treatment of the monolithium compound 2 with n-BuLi and K (or KC8) gave [t-BuNPNt-Bu]Li center dot(tmeda) (17) and{[t-BuNPNt-Bu] K(tmeda)}(2) (18), respectively. bond covalent radii; hexacoordinated group-14 elements; phosphorus donor ligands; x-ray structures; structural-characterization; cyclic diazastannylenes; single-bond; complexes; reactivity; germanium(ii)

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