Addition of Enolisable Ketones to (dpp‐bian)Mg(THF)3 [dpp‐bian =1,2‐Bis{(2,6‐diisopropylphenyl)imino}acenaphthene]

The enolates [(dpp-bian)(H)]Mg[OC(=CHPh)CH2Ph](THF)2 (6), [(dpp-bian)(H)]Mg[OC(=CPh2)CH3](THF)2 (7) and [(dpp-bian)(H)]Mg(camphor)(py)2 (8) were prepared by treating (dpp-bian)Mg(THF)3 (1) with equimolar amounts of dibenzyl ketone, 1,1-diphenylacetone and camphor, respectively. Single-crystal X-ray structure analyses showed these enolates to be five-coordinate, trigonal bipyramidal magnesium complexes with terminal, nonbridging enolate ligands. In solutions of 6 and 7 the proton, which in the solid-state is attached to only one of the two nitrogen atoms of the dpp-bian ligand, is delocalised between both nitrogen atoms. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

[1]  M. Hummert,et al.  Reductive Isopropyl Radical Elimination from (dpp-bian)Mg-iPr(Et2O) , 2005 .

[2]  M. Hummert,et al.  Reactions of (dpp-BIAN)Mg(thf)3 complex (dpp-BIAN is 1,2-bis{(2,6-diisopropylphenyl)imino}acenaphthene) with halogen-containing reagents , 2004 .

[3]  V. Cherkasov,et al.  Divalent germanium compound with a radical-anionic ligand: molecular structures of (dpp-BIAN)*- GeCl and its hydrochloration products [(dpp-BIAN)(H)2]*+ [GeCl3]- and [[(dpp-BIAN)(H)2*+]2(Cl-)]+ [GeCl3]- (dpp-BIAN=1,2-Bis[(2,6-diisopropylphenyl)imino]acenaphthene). , 2004, Inorganic chemistry.

[4]  M. Hummert,et al.  Stable Germylenes Derived from 1,2-Bis(arylimino)acenaphthenes , 2004 .

[5]  G. Fukin,et al.  Monomeric Magnesium and Calcium Complexes containing the Rigid, Dianionic 1, 2‐Bis[(2, 5‐di‐tert‐butylphenyl)imino]acenaphthene (dtb‐BIAN) and 1, 2‐Bis[(2‐biphenyl)imino]acenaphthene (bph‐BIAN) Ligands , 2004 .

[6]  G. Fukin,et al.  Reduction of 1,2-Bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) with Alkali Metals − A Study of the Solution Behaviour of (dpp-bian)n−[M+]n (M = Li, Na; n = 1−4) with UV/Vis, ESR and 1H NMR Spectroscopy , 2004 .

[7]  S. Nolan,et al.  Catalytic activity of Pd(II) and Pd(II)/DAB-R systems for the Heck arylation of olefins , 2003 .

[8]  V. Cherkasov,et al.  Reduction of benzophenone and 9(10H)-anthracenone with the magnesium complex [(2,6-iPr2C6H3-bian)Mg(thf)3]. , 2003, Chemistry.

[9]  G. Coates,et al.  Chiral anilines: development of C2-symmetric, late-transition metal catalysts for isoselective 2-butene polymerization. , 2003, Chemical communications.

[10]  G. Fukin,et al.  Monomeric Magnesium and Calcium Complexes Containing the Bidentate, Dianionic 1,2-Bis[(2,6-diisopropylphenyl)imino]acenaphthene Ligand , 2003 .

[11]  W. Kaminsky,et al.  Ethene/norbornene copolymerization with palladium(II) alpha-diimine catalysts: from ligand screening to discrete catalyst species. , 2003, Chemistry.

[12]  M. Brookhart,et al.  Mechanistic studies of nickel(II) alkyl agostic cations and alkyl ethylene complexes: investigations of chain propagation and isomerization in (alpha-diimine)Ni(II)-catalyzed ethylene polymerization. , 2003, Journal of the American Chemical Society.

[13]  L. Giordano,et al.  Cyclopentene-regioselective palladium-catalyzed cycloisomerization under neutral and bis-cationic reaction conditions , 2003 .

[14]  J. Gallucci,et al.  Coordination chemistry and reactivity of monomeric alkoxides and amides of magnesium and zinc supported by the diiminato ligand CH(CMeNC(6)H(3)-2,6-(i)Pr(2))(2). A comparative study. , 2002, Inorganic chemistry.

[15]  Y. Fukuda,et al.  Mixed-Ligand Copper(II) Complexes with the Rigid Bidentate Bis(N-arylimino)acenaphthene Ligand: Synthesis, Spectroscopic-, and X-ray Structural Characterization , 2001 .

[16]  S. Teat,et al.  Synthesis and structural characterisation of a magnesium bisenolate: a tetrameric (Mg2O2)(2) chain terminated by solvating ketone , 2000 .

[17]  Martijn W. van Laren,et al.  Selektive Palladium(0)‐katalysierte homogene Hydrierung von Alkinen zu (Z)‐Alkenen , 1999 .

[18]  K. Henderson,et al.  Bis(amido)magnesium mediated aldol additions: first structural characterisation of an amidomagnesium aldolate intermediate , 1999 .

[19]  W. Clegg,et al.  Solvent effects and molecular rearrangements during the reaction of Hauser bases with enolisable ketones: structural characterisation of [{ButC(=CH2)OMgBr.HMPA}2] and [MgBr2.(HMPA)2] , 1998 .

[20]  H. Hoffmann,et al.  Katalytische Drei‐Komponenten‐Synthese von konjugierten Dienen aus Alkinen über Pd0‐, PdII‐ und PdIV‐(1,2‐Diimin)‐Zwischenstufen , 1997 .

[21]  George M. Sheldrick,et al.  SADABS, Program for Empirical Absorption Correction of Area Detector Data , 1996 .

[22]  J. Salvino,et al.  X-Ray crystal structure determination of a bromomagnesium ketone enolate , 1986 .