Synthesis and coordination chemistry of enantiopure t-BuMeP(O)H. Issue 15 (28th March 2018)

• Record Type: Journal Article
• Authors: Gallen, Albert; Orgué, Sílvia; Muller, Guillermo; Escudero-Adán, Eduardo C.; Riera, Antoni; Verdaguer, Xavier; Grabulosa, Arnald
• Is Part Of: Dalton transactions. Volume 47:Issue 15(2018)
• Page Start: 5366
• Page End: 5379
• Publication Date: 2018-03-28
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt00897c
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Enantioselective synthesis of t -BuMeP(O)H and its coordination chemistry towards several transition metals are described, showing a variety of coordination modes. 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)(κ P -( R )-1 )] (M = Ir, Rh;4 and7 respectively) have been detected in solution but could not be isolated while trans -[RhCl(CO)(κ P -( S )-1 )2 ] (9 ) has been successfully obtained in good yield. Gold complex [AuCl(κ P -( S )-1 )] (10 ) has been prepared and its crystal structure shows the presence of aurophilic interactions. Three new ruthenium complexes ([RuCl2 (η 6 - p -cymene)(κ P -( R )-1 )], 12 ), ([RuCl2 (CO)3 (κ O -( S )-1 )], 13 ) and trans -([RuCl2 (CO)2 (κ P -( S )-1 )2 ], 14 ) have been synthesised and fully characterised, including the crystal structure of12 . Four palladium coordination compounds have been prepared: trans -[PdCl2 (κ P -( S )-1 )2 ] ( trans -15 ), [Pd(μ-Cl)(κ P -( S )-1 )2 ]2 (16·OH and16·BF2 ) and [Pd(μ-OAc)(κ P -( S )-1 )2 ] (17 ) and the crystal structure of complex16·OH proves the pseudobidentate coordination of the two molecules of1 . Three organometallic allylpalladium complexes have been prepared namely [Pd(η 3 -Ph2 C2 H3 )Cl(κ P -( S )-1 )] (18 ) and [Pd(η 3 -Ph2 C2 H3 )(κ P -( S )-1 )2 ] (19·OH and19·BF2 ). The crystal structure of19·BF2 constitutes the first allylpalladium-SPO complex reported to date.