Hydrophosphination reactions with transition metal ferrocenylphosphine complexes. Issue 5 (18th November 2015)

• Record Type: Journal Article
• Authors: Pritzwald-Stegmann, Julian Rodger Frederic; Lönnecke, Peter; Hey-Hawkins, Evamarie
• Is Part Of: Dalton transactions. Volume 45:Issue 5(2016)
• Page Start: 2208
• Page End: 2217
• Publication Date: 2015-11-18
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c5dt03374h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : The group 6 metal mono-, bis- and tris-ferrocenylphosphine complexes [M(CO)5 (PH2 Fc)], cis -[M(CO)4 (PH2 Fc)2 ] and fac -[M(CO)3 (PH2 Fc)3 ] (M = Cr, Mo, W; Fc = Fe(η 5 -C5 H4 )(η 5 -C5 H5 )) were prepared and fully characterised. The coordinated FcPH2 ligand of [W(CO)5 (PH2 Fc)] undergoes hydrophosphination with alkene substrates bearing EWGs, yielding the corresponding secondary phosphine complexes. Abstract : The group 6 metal mono-, bis- and tris-ferrocenylphosphine complexes [M(CO)5 (PH2 Fc)] (1a, M = Cr;1b, M = Mo;1c, M = W), cis -[M(CO)4 (PH2 Fc)2 ] (2a, M = Cr;2b, M = Mo;2c, M = W) and fac -[M(CO)3 (PH2 Fc)3 ] (3a, M = Cr;3b, M = Mo;3c, M = W) [Fc = Fe(η 5 -C5 H4 )(η 5 -C5 H5 )] were prepared and fully characterised. IR and NMR spectroscopy and single-crystal X-ray diffraction analysis indicate that FcPH2 is as good a σ donor as PhPH2 but is easier to handle and furthermore has a redox-active ferrocenyl group. Complex1c was employed in the hydrophosphination of acrylonitrile and methyl acrylate in the presence of catalytic amounts of KO t Bu giving the secondary phosphine complexes [W(CO)5 {PH(Fc)(CH2 CH2 CN)}] (4a ) and [W(CO)5 {PH(Fc)(CH2 CH2 C(O)OMe)}] (4b ). In addition, FcP(CH2 CH2 CN)2 (5 ) was prepared by a similar method from FcPH2 and acrylonitrile. These hydrophosphination products represent a convenient method for the modification of phosphines.