New phosphaneborane chemistry

Hubert Schmidbaur

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115 Scopus citations


Following a short account of pertinent literature, recent work on two classes of phosphaneboranes is summarized. H3B(CH3)2PCl (1) was found to be an excellent precursor for an extended new chemistry of the H3B(CH3)2P-group, which is isoelectronic with the (CH3)3Si-group. Boranatodimethylphosphinic acid H3B(CH3)2POH, its anhydride H3B(CH3)2POP(CH3)2BH3, salts, complexes, esters and carboxylates have been prepared and identified through analytical and spectroscopic studies. The corresponding sulphur analogues are also available. The amide H3B(CH3)2PNH2 is formed from 1 and NH3 as a stable crystalline product. It is easily converted into its imide H3B(CH3)2PNHP(CH3)2BH3 and a variety of organic derivatives. H3B(CH3)2PCH2P(CH3)2BH3 has protic hydrogen atoms in the CH2 bridge and affords a crystalline ylidic Li salt, the crystal structure of which was determined. CH3 metallation of (CH3)3PBH3 leads to similar product useful for derivatisation. The (CH3)3PBH2P(CH3)3+X salts are starting materials for the preparation of the novel CH2(CH3)2PBH2P(CH3)2CH2 ligand system. Its coordination chemistry, with examples from most groups of the Periodic Table, is reviewed, including both diamagnetic and paramagnetic species. Representative structures were determined by X-ray diffraction, and multi-nuclei NMR and magnetic data were used for further characterisation.

Original languageEnglish
Pages (from-to)287-306
Number of pages20
JournalJournal of Organometallic Chemistry
Issue number1
StatePublished - 1980
Externally publishedYes


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