Issue 15, 2018

Synthesis and coordination chemistry of enantiopure t-BuMeP(O)H

Abstract

Both enantiomers of the optically pure Secondary Phosphine Oxide (SPO) t-BuMeP(O)H (1) have been obtained by deboronation of phosphinous acid-borane t-BuMeP(O)H·BH3 (3) with HBF4 followed by hydrolysis of the intermediate adduct t-BuMeP(O)H·BF3 (1·BF3), which has been isolated and crystallographically characterised. Complexes [MCl(COD)(κP-(R)-1)] (M = Ir, Rh; 4 and 7 respectively) have been detected in solution but could not be isolated while trans-[RhCl(CO)(κP-(S)-1)2] (9) has been successfully obtained in good yield. Gold complex [AuCl(κP-(S)-1)] (10) has been prepared and its crystal structure shows the presence of aurophilic interactions. Three new ruthenium complexes ([RuCl26-p-cymene)(κP-(R)-1)], 12), ([RuCl2(CO)3O-(S)-1)], 13) and trans-([RuCl2(CO)2P-(S)-1)2], 14) have been synthesised and fully characterised, including the crystal structure of 12. Four palladium coordination compounds have been prepared: trans-[PdCl2P-(S)-1)2] (trans-15), [Pd(μ-Cl)(κP-(S)-1)2]2 (16·OH and 16·BF2) and [Pd(μ-OAc)(κP-(S)-1)2] (17) and the crystal structure of complex 16·OH proves the pseudobidentate coordination of the two molecules of 1. Three organometallic allylpalladium complexes have been prepared namely [Pd(η3-Ph2C2H3)Cl(κP-(S)-1)] (18) and [Pd(η3-Ph2C2H3)(κP-(S)-1)2] (19·OH and 19·BF2). The crystal structure of 19·BF2 constitutes the first allylpalladium-SPO complex reported to date.

Graphical abstract: Synthesis and coordination chemistry of enantiopure t-BuMeP(O)H

Supplementary files

Article information

Article type
Paper
Submitted
08 Mar 2018
Accepted
20 Mar 2018
First published
21 Mar 2018

Dalton Trans., 2018,47, 5366-5379

Synthesis and coordination chemistry of enantiopure t-BuMeP(O)H

A. Gallen, S. Orgué, G. Muller, E. C. Escudero-Adán, A. Riera, X. Verdaguer and A. Grabulosa, Dalton Trans., 2018, 47, 5366 DOI: 10.1039/C8DT00897C

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