B-substituted group 1 phosphides: synthesis and reactivity

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F23%3A39920977" target="_blank" >RIV/00216275:25310/23:39920977 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlepdf/2023/dt/d3dt02568c" target="_blank" >https://pubs.rsc.org/en/content/articlepdf/2023/dt/d3dt02568c</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d3dt02568c" target="_blank" >10.1039/d3dt02568c</a>

Jazyk výsledku

angličtina

Název v původním jazyce

B-substituted group 1 phosphides: synthesis and reactivity

Popis výsledku v původním jazyce

1-Boryl-8-phosphinonaphthalenes 1-BCy2-8-PCl2-C10H6 (1) and 1-BCy2-8-PPhCl-C10H6 (2) were prepared and used as starting materials for the synthesis of B-substituted phosphides. The reduction of 1 and 2 by Mg provided neutral compounds [1-BCy-8-PCy-C10H6]2 (3) and [1-BCy2-8-PPh-C10H6]2 (4). Compound 3 represents the dimer of phosphinoborane 1-BCy-8-PCy-C10H6 while complex 4 is a rare example of a discrete B &lt;- P coordinated diphosphine. The reduction of 2 by Na or K in THF yielded B-substituted group 1 phosphides [Na(THF)3]+[1-BCy2-8-PPh-C10H6]- (5) and {[K(THF)2]+[1-BCy2-8-PPh-C10H6]-}infinity (6), which structurally resembled bulky group 1 phosphides. Complex 5 showed easy activation of elemental chalcogens E (E = O, S, Se) to give B-substituted chalcogenophosphinites {[Na(THF)2]+[1-BCy2-8-P(E)Ph-C10H6]}2 (E = O (7), S (8), Se (9)) as the products of chalcogen insertion into the P-Na bond. Importantly no oxidation to dichalcogenophosphinates was observed. Compound 5 is tolerant of the C=O polar bonds in organic substrates and the reactions of 5 with 2,3-butanedione or an acyl chloride provided {[Na(THF)2]+[1-BCy2-8-P{CHC(O)C(Me)O}Ph-C10H6]-}2 (10) and [1-BCy2-8-P{C(O)tBu}Ph-C10H6] (11). Finally, B-coordinated phosphatetrylenes [1-BCy2-8-P(SnL)Ph-C10H6] (12) and [1-BCy2-8-P(PbL)Ph-C10H6] (13) (L is {2,6-(Me2NCH2)C6H3}-) were also prepared by substitution reactions of 5. B-substituted group 1 phosphides were prepared. They showed interesting reactivity with elemental chalcogens E (E = O, S, Se), organic substrates and organometallic halides.

Název v anglickém jazyce

B-substituted group 1 phosphides: synthesis and reactivity

Popis výsledku anglicky

1-Boryl-8-phosphinonaphthalenes 1-BCy2-8-PCl2-C10H6 (1) and 1-BCy2-8-PPhCl-C10H6 (2) were prepared and used as starting materials for the synthesis of B-substituted phosphides. The reduction of 1 and 2 by Mg provided neutral compounds [1-BCy-8-PCy-C10H6]2 (3) and [1-BCy2-8-PPh-C10H6]2 (4). Compound 3 represents the dimer of phosphinoborane 1-BCy-8-PCy-C10H6 while complex 4 is a rare example of a discrete B &lt;- P coordinated diphosphine. The reduction of 2 by Na or K in THF yielded B-substituted group 1 phosphides [Na(THF)3]+[1-BCy2-8-PPh-C10H6]- (5) and {[K(THF)2]+[1-BCy2-8-PPh-C10H6]-}infinity (6), which structurally resembled bulky group 1 phosphides. Complex 5 showed easy activation of elemental chalcogens E (E = O, S, Se) to give B-substituted chalcogenophosphinites {[Na(THF)2]+[1-BCy2-8-P(E)Ph-C10H6]}2 (E = O (7), S (8), Se (9)) as the products of chalcogen insertion into the P-Na bond. Importantly no oxidation to dichalcogenophosphinates was observed. Compound 5 is tolerant of the C=O polar bonds in organic substrates and the reactions of 5 with 2,3-butanedione or an acyl chloride provided {[Na(THF)2]+[1-BCy2-8-P{CHC(O)C(Me)O}Ph-C10H6]-}2 (10) and [1-BCy2-8-P{C(O)tBu}Ph-C10H6] (11). Finally, B-coordinated phosphatetrylenes [1-BCy2-8-P(SnL)Ph-C10H6] (12) and [1-BCy2-8-P(PbL)Ph-C10H6] (13) (L is {2,6-(Me2NCH2)C6H3}-) were also prepared by substitution reactions of 5. B-substituted group 1 phosphides were prepared. They showed interesting reactivity with elemental chalcogens E (E = O, S, Se), organic substrates and organometallic halides.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA23-06548S" target="_blank" >GA23-06548S: Superhydrofobní materiály na bázi heteroboroxinů</a><br>

Návaznosti

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

Rok uplatnění

2023

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

1477-9234

Svazek periodika

52

Číslo periodika v rámci svazku

45

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

16

Strana od-do

"16870–16885"

Kód UT WoS článku

001091864500001

EID výsledku v databázi Scopus

2-s2.0-85176109719