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B-substituted group 1 phosphides: synthesis and reactivity
Year: 2023
Type of publication: článek v odborném periodiku
Name of source: Dalton Transactions
Publisher name: Royal Society of Chemistry
Place: Cambridge
Page from-to: 16870–16885
Titles:
Language Name Abstract Keywords
cze B-substituovan0 fosfidy prvků 1 skupiny: Syntéza a reaktivita 1-Boryl-8-fosfinonaftaleny 1-BCy2-8-PC12-C10H6 (1) a 1-BCy2-8-PPhCl-C10H6 (2) byly připraveny a použity jako výchozí materiály pro syntézu B-substituovaných fosfidů B-substituované fosfidy;syntéza;reaktivita
eng B-substituted group 1 phosphides: synthesis and reactivity 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 <- 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. alkali-metal complexes; X/ray crystal-structure; lithium complexes; pi interactions; potassium; boron; ligand

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