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]−}∞ (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 CO 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. [ABSTRACT FROM AUTHOR]