A hydroboration route to geminal P/B frustrated Lewis pairs with a bulky secondary phosphane component and their reaction with carbon dioxide. Issue 35 (22nd August 2017)

• Record Type: Journal Article
• Authors: Jian, Zhongbao; Kehr, Gerald; Daniliuc, Constantin G.; Wibbeling, Birgit; Erker, Gerhard
• Is Part Of: Dalton transactions. Volume 46:Issue 35(2017)
• Page Start: 11715
• Page End: 11721
• Publication Date: 2017-08-22
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c7dt02315d
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The hydroboration of a secondary alkynyl phosphane gives a geminal P/B frustrated Lewis pair that reacts with carbon dioxide. Abstract : The secondary aryl-P(H) phosphanyl substituted tert -butylacetylenes7a, b (aryl: Mes or Mes*) undergo hydroboration with [HB(C6 F5 )2 ] to give the geminal vinylidene-bridged P/B Lewis pairs8a, b . The treatment of8a, b with benzonitrile, N -sulfinylaniline, and phenyl isothiocyanate, respectively, gives the addition products12a, b, 13a, b, and14 with proton transfer from the phosphorus to the more basic nitrogen site. The reaction of the FLPs8a, b with carbon dioxide yields a doubly boron bonded addition product. The reaction of8b with a conjugated ynone formally proceeded by trans -1, 2-hydrophosphination of the alkyne at the geminal FLP framework to give the seven-membered heterocycle21 .