The phosphinoboration of acyl chlorides

• Published in: Dalton transactions : an international journal of inorganic chemistry 2020-04, Vol.49 (16), p.592-599
• Main Authors: Murphy, Maia C, Trofimova, Alina, LaFortune, James H. W, Vogels, Christopher M, Geier, Stephen J, Binder, Justin F, Macdonald, Charles L. B, Stephan, Douglas W, Westcott, Stephen A
• Format: Article
• Language: English
• Subjects: Aliphatic compounds; Aromatic compounds; Boron compounds; Chlorides; Crystallography; Esters; High temperature; Phosphines; Rhodium
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d0dt00579g

This investigation examines the reactivity of phosphinoboronate esters Ph 2 PBpin (pin = 1,2-O 2 C 2 Me 4 ) and Ph 2 PBcat (cat = 1,2-O 2 C 6 H 4 ), as well as other phosphinoboron species, with various aryl and aliphatic acyl chlorides. These reactions proceed smoothly to give acyl phosphines of the type RC(O)PR′ 2 along with loss of a boron-chloride compound. In some cases, a second equivalent of the phosphinoboron species can add to the C&z.dbd;O double bond at elevated temperatures to give the corresponding diphosphines RC(OBR′′ 2 )(PR′ 2 ) 2 . These ambiphilic diphosphines behave like substituted (1,1-bis(diphenylphosphino)methane) derivatives in a reaction of PhC(OBpin)(PPh 2 ) 2 ( 2a ) with (η 5 -C 9 H 7 )Rh(η 2 -coe) 2 (coe = cis -cyclooctene) affording the indenyl rhodium complex (η 5 -C 9 H 7 )Rh(PhC(OBpin)(PPh 2 ) 2 ) ( 3a ) where the phosphines are bound to the metal centre in a κ 2 -P,P bidentate manner. This investigation examines the reactivity of phosphinoboronate esters Ph 2 PBpin (pin = 1,2-O 2 C 2 Me 4 ) and Ph 2 PBcat (cat = 1,2-O 2 C 6 H 4 ), as well as other phosphinoboron species, with various aryl and aliphatic acyl chlorides.