The C_α‐Deprotonated Iminophosphorane Ph₂P(CH₂Py)(NSiMe₃) as an N,N‐Chelating Ligand for Iron and Zinc

Abstract

The iminophosphorane Ph2P(CH2Py)(NSiMe3) (Py = NC5H4) is deprotonated at the Cα‐position in a reaction with [M{N(SiMe3)2}2] (M = Fe2+, Zn2+) to give metallaspirocycles in which the metal cations are N,N‐chelated by the ring‐ and imino‐nitrogen atoms of both monoanionic ligands. The molecular structures of [M{Ph2P(CHPy)(NSiMe3)}2] [M = Fe (1), Zn (2)] are discussed and general trends in the bonding of the [Ph2P(CHPy)(NSiMe3)]− anion on metal coordination are deduced. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Heteroaromatic Substituted Phosphoranes with Enhanced Hemilabile Character

“…Aiming for a new coordination site with a Lewis hardness different from that of the known diphenyl-2-picolyliminophosphorane, we oxidized diphenyl-2-picolylphosphane with sulfur and gray selenium (Scheme ). The resulting ligands are thought to have similar properties according to the concept of Langmuir, since iminophosphoranes are isoelectronic with thiophosphoranes .…”

Synthesis and characterisation of six Fe(II or III), Co(II) or Zr(IV) complexes containing the ligand [CH(SiMe2R)P(Ph)2NSiMe3]− (R=Me, NEt2) and of [Co{N(SiMe3)C(Ph)C(H)P(Ph)2NSiMe3}2]

“…A lithium derivative, prepared in situ from R 1 CH 2 P(Ph) 2 =NPh and successively LiNPr i 2 and a cyanoarene, was used for various organic transformations [9]. An iron(II) complex [Fe(C 0 ) 2 ] was obtained from [Fe{N(SiMe 3 ) 2 } 2 ] and 2 HC 0 [10]. As shown by one of us, novel Ni(II) complexes, bearing a monoanionic P,N,P-, P,N,N-, or N,N,N-pincer ligand containing the ligand C 00 , were effective catalysts for Kumada cross-coupling reactions [11].…”

Synthesis, Structures, and Magnetic Properties of N‐Trialkylsilyl‐8‐amidoquinoline Complexes of Chromium, Manganese, Iron, and Cobalt as well as of Wheel‐Like Hexanuclear Iron(II) and Manganese(II) Bis(8‐amidoquinoline)

“…Recent examples include the oxidative dehydrogenation of 2-pyridylmethylamines at iron [14] or cobalt [15,16] as well as of 2-pyridylmethylphosphanes. [17][18][19] Even dimethylzinc is able to oxidize shielded (2-pyridylmethyl)(trialkylsilyl)amides to yield 1,2-bis(2-pyridyl)-1,2-bis(trialkylsilylamido)bis(methylzinc) according to Equation (1). [20,21] These side reactions can be avoided by employing the related 8-aminoquinoline, which allows the investigation of the coordination behavior of these ligands.…”