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Dimeric Phosphinoboranes [R′(Hal)B‐PHR] 2 and some of their Reactions
Author(s) -
Jetzfellner Ralf,
Nöth Heinrich,
Paine Robert T.
Publication year - 2007
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200700070
Subject(s) - chemistry , medicinal chemistry , stereochemistry , halide , bicyclic molecule , cyclobutanes , ether , lithium (medication) , ring (chemistry) , cyclobutane , organic chemistry , medicine , endocrinology
Reactions of organylboron halides RBX 2 (R = t Bu, i Pr, Et, Me; X = Cl, Br) with lithium organylphosphides LiPHR′ (R′= mes, Ph, t Bu) in a 1:1 ratio lead to the corresponding 1,3,2,4‐diphospha‐dibora‐cyclobutanes [R′(H)P‐B(Hal)R] 2 . Further substitution to 2,4‐diphosphino derivatives has only be achieved for [ t Bu(H)P‐B( t Bu)PH t Bu] 2 ( 12 ). Its exocyclic PH t Bu groups can be metallated by LiPH t Bu, but it is more convenient to use the 1 : 3 reaction of t BuBCl 2 with LiPH t Bu for the preparation of [ t Bu(H)P‐B( t Bu)PLi t Bu] 2 ( 16 ), which was isolated as a diethyl ether solvate. Compound 12 on irradiation with a mercury vapour lamp splits off t BuPH 2 and generates the bicyclic t BuP[B t Bu‐PH t Bu] 2 ( 17 ). The new compounds have been characterized by NMR and Mass spectral data. The t Bu groups of compound [Br( t Bu)B‐PH t Bu] 2 ( 7 ), are present in an all‐ trans ‐configuration. Its B 2 P 2 ring is planar.