Synthesis and Structural Characterizations of para-bis(dialkyl/ diarylphosphino)phenylenes Built Around Tetrahalogenated Benzene Cores

Document Type

Article

Publication Date

8-2005

Department

Department of Chemistry

Abstract

Double deprotonation of 1,2-dibromo-4,5-difluorobenzene and 1-bromo-2-chloro-4,5-difluorobenzene by lithium diisopropylamide (LDA) in ethereal solutions is facile at very low temperatures (T<-90 °C). The organo-dilithium intermediates thus generated react readily with chlorophosphines ClPR2 (R=Ph and/or iPr), producing 1,2-dibromo-3,6-bis(diphenylphosphino)-4,5-difluorobenzene (1a), 1,2-dibromo-3,6-bis(diisopropylphosphino)-4,5-difluorobenzene (1b) and 1-bromo-2-chloro-3,6-bis(diphenylphosphino)-4,5-difluorobenzene (1c). Corresponding P-oxides 2a-c are obtained by oxidation of 1a-c with H2O2. Analogous reactions of 1,2-dibromo-4,5- difluorobenzene and 1-bromo-2-chloro-4,5-difluorobenzene with only 1 equiv. of LDA do not result in selective monodeprotonations, as 1a and 1c are formed preferentially after ClPPh2 quench. All of the isolated new compounds were fully characterized by multinuclear NMR spectroscopy, elemental analysis and/or mass-spectrometry. In addition, 1a, 1c, 2a, and 2b were characterized by single crystal X-ray diffraction methods.

Publisher's Statement

© 2005 Elsevier B.V. All rights reserved.

Publication Title

Inorganica Chimica Acta

Link to Full Text

Share

COinS