Germylenes and stannylenes stabilized within N2PE rings (E = Ge or Sn): combined experimental and theoretical study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F16%3A39902107" target="_blank" >RIV/00216275:25310/16:39902107 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1039/c6dt01616b" target="_blank" >http://dx.doi.org/10.1039/c6dt01616b</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c6dt01616b" target="_blank" >10.1039/c6dt01616b</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Germylenes and stannylenes stabilized within N2PE rings (E = Ge or Sn): combined experimental and theoretical study

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Germylenes and stannylenes stabilized within N2PE rings (E = Ge or Sn): combined experimental and theoretical study

Popis výsledku anglicky

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.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CA - Anorganická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GAP207%2F12%2F0223" target="_blank" >GAP207/12/0223: Hybridní ligandy pro stabilizaci/specifickou aktivaci kovových center v nízkých oxidačních stavech.</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2016

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Dalton Transactions

ISSN

1477-9226

e-ISSN

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Svazek periodika

45

Číslo periodika v rámci svazku

25

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

12

Strana od-do

10343-10354

Kód UT WoS článku

000378392200029

EID výsledku v databázi Scopus

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