Coordination chemistry with phosphine and phosphine oxide-substituted hydroxyferrocenes.

New unsymmetrical hydroxyferrocenes were synthesised from dibromoferrocene. The oxygen heteroatom was introduced via lithiation and quenching with bis-trimethylsilylperoxide followed by hydrolysis to unmask the hydroxyl functionality. The coordination chemistry of 1'-(diphenylphosphino)-1-hydroxyferrocene 2 was explored with palladium and rhodium precursors. A dinuclear palladium methyl complex with bridging ferrocenyloxo groups was obtained from the reaction between 2 and (cyclooctadiene)methylchloropalladium(II). With tetracarbonyldichlorodirhodium(I), two complexes were isolated. The major product was a bis ligand cis phosphine ligated complex with one ligand bound in a chelating mode and one with a pendant hydroxyl group. A minor product was crystallographically characterised as a dinuclear ferrocenyloxo-bridged rhodium carbonyl complex. The coordination chemistry of 2 and the corresponding phosphine oxide 3 was examined with group 4 metals and the resulting complexes examined as ethylene polymerisation catalysts. The ligands were found to bind in either a chelating fashion or with pendant phosphine donors. In all cases, low to moderately active ethylene polymerisation catalysts were found. The catalysts were very unstable and catalyst residues were observed in the isolated polymer indicating a short catalyst lifetime.

[1]  I. Císařová,et al.  Preparation and structural characterization of simple and donor-substituted triorganostannyl 1'-(diphenylphosphino)-1-ferrocenecarboxylates and their P-chalcogenide derivatives , 2010 .

[2]  P. Braunstein,et al.  Tridentate assembling ligands based on oxazoline and phosphorus donors in dinuclear Pd(I)-Pd(I) complexes. , 2009, Inorganic chemistry.

[3]  S. Doherty,et al.  Synthesis of Biaryl Diphosphines via a Stepwise Regioselective Double Diels-Alder Cycloaddition Elimination Sequence: Efficient Ligands for the Palladium-Catalyzed Amination of Aromatic Bromides , 2009 .

[4]  I. Císařová,et al.  Phosphinoferrocenyl Carboxamides Bearing Glycine Pendant Groups: Synthesis, Palladium(II) Complexes, and Catalytic Use in Polar and Aqueous Reaction Media , 2009 .

[5]  P. Braunstein,et al.  Palladium Alkyl Complexes Containing β-Phosphonato−Phosphine P,O Ligands and Their Reactivity toward CO-Ethylene or -Acrylate Insertion , 2009 .

[6]  G. Giambastiani,et al.  Nickel Complexes with Phosphinito-Oxazoline Ligands: Temperature-Controlled Formation of Mono- or Dinuclear Complexes and Catalytic Oligomerization of Ethylene and Propylene , 2009 .

[7]  A. White,et al.  Zirconium Complexes Containing Tetradentate O,P,P,O Ligands: Ethylene and Propylene Polymerization Studies , 2008 .

[8]  Martin J. Hanton,et al.  Rigid N-Phosphino Guanidine P,N Ligands and Their Use in Nickel-Catalyzed Ethylene Oligomerization , 2008 .

[9]  C. Bianchini,et al.  Palladium(II) Complexes with Phosphanylferrocenecarboxylate Ligands and Their Use as Catalyst Precursors for Semialternating CO–Ethylene Copolymerization , 2008 .

[10]  A. White,et al.  Group 4 Metal Olefin Polymerization Catalysts Stabilized by Bidentate O,P Ligands , 2008 .

[11]  A. White,et al.  Redox control within single-site polymerization catalysts. , 2006, Journal of the American Chemical Society.

[12]  T. Hor,et al.  1,1'-P/O-ferrocenyl ligands in palladium-catalyzed suzuki coupling of aryl chlorides , 2006 .

[13]  U. Siemeling,et al.  1,1'-Di(heteroatom)-functionalised ferrocenes as [N,N], [O,O] and [S,S] chelate ligands in transition metal chemistry. , 2005, Chemical Society reviews.

[14]  G. Giambastiani,et al.  Progress in stereoselective catalysis by metal complexes with chiral ferrocenyl phosphines , 2004 .

[15]  David J. Williams,et al.  Novel unsymmetrical P/O substituted ferrocene ligands and the first structurally characterised hydroxyferrocene derivative. , 2004, Dalton transactions.

[16]  N. Long,et al.  The syntheses and catalytic applications of unsymmetrical ferrocene ligands. , 2004, Chemical Society reviews.

[17]  David J. Williams,et al.  Synthesis, Coordination Chemistry, and Catalytic Application of a Novel Unsymmetrical P/O Ferrocenediyl Ligand , 2004 .

[18]  M. Brookhart,et al.  Polymerization and oligomerization of ethylene by cationic nickel(II) and palladium(II) complexes containing bidentate phenacyldiarylphosphine ligands , 2003 .

[19]  Thomas J. Colacot,et al.  A concise update on the applications of chiral ferrocenyl phosphines in homogeneous catalysis leading to organic synthesis. , 2003, Chemical reviews.

[20]  C. Elschenbroich,et al.  [5]Trovacenol, (η7-C7H7)V(η5-C5H4OH): Synthesis and Structural Characterization†,1 , 2002 .

[21]  M. Brookhart,et al.  Ethylene Polymerization and Ethylene/Methyl 10-Undecenoate Copolymerization Using Nickel(II) and Palladium(II) Complexes Derived from a Bulky P,O Chelating Ligand , 2002 .

[22]  Charlotte K. Williams,et al.  The Synthesis and Metal Coordination Chemistry of a Novel Phosphine- and Thiolate-Substituted Ferrocenediyl Ligand , 2002 .

[23]  A. Shafir,et al.  Stabilization of a cationic Ti center by a ferrocene moiety: a remarkably short Ti-Fe interaction in the diamide ([(eta(5)-C(5)H(4)NSiMe(3))(2)Fe]TiCl)(2)(2+). , 2001, Journal of the American Chemical Society.

[24]  Fr'ed'eric Naud,et al.  Hemilability of Hybrid Ligands and the Coordination Chemistry of Oxazoline-Based Systems. , 2001, Angewandte Chemie.

[25]  David J. Williams,et al.  The synthesis and metal coordination chemistry of new 1,1′-N-substituted ferrocenediyl ligands derived from 1,1′-diaminoferrocene , 2001 .

[26]  T. Dong,et al.  Selective Monolithiation of 1,1-Dibromoferrocene Applied to the Synthesis of New Unsymmetrical 1,1-Disubstituted Ferrocenyl Ligands , 2000 .

[27]  Charlotte K. Williams,et al.  New unsymmetrical thioether- and thiolate-substituted ferrocene ligands and an unusual bridged-Pd dimer complex , 2000 .

[28]  C. Richards,et al.  The first example of an enantiopure planar chiral hydroxyferrocene ligand , 1999 .

[29]  David J. Williams,et al.  Synthesis and characterisation of 1-(diphenylphosphino)-1′-(methylsulfanyl)ferrocene and a series of metal (CuI, AgI)–ferrocenylene complexes , 1999 .

[30]  C. Mirkin,et al.  Ligand Design for Electrochemically Controlling Stoichiometric and Catalytic Reactivity of Transition Metals. , 1998, Angewandte Chemie.

[31]  M. Herberhold,et al.  Neue Derivate des Ferrocenols und 1,1'-Ferrocendiols , 1998 .

[32]  I. Butler,et al.  The synthesis and characterisation of heterosubstituted aminoferrocenes , 1998 .

[33]  I. Císařová,et al.  Synthesis, characterization and structure of rhodium(I) carbonyl complexes with O,P-chelating 1′-(diphenylphosphino)ferrocenecarboxylate or P-monodentate 1′-(diphenylphosphino)ferrocenecarboxylic acid , 1998 .

[34]  H. Kagan,et al.  An Efficient Asymmetric Synthesis of 2-Substituted Ferrocenecarboxaldehydes , 1997 .

[35]  D. J. Tempel,et al.  Living Polymerization of α-Olefins Using NiII−α-Diimine Catalysts. Synthesis of New Block Polymers Based on α-Olefins , 1996 .

[36]  I. Butler,et al.  A Rapid Convenient Synthesis of Ferrocene-Based Triphos Analogue Ligands , 1996 .

[37]  Maurice Brookhart,et al.  New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and .alpha.-Olefins , 1995 .

[38]  A. Börner.  Ferrocenes. Homogeneous Catalysis – Organic Synthesis – Material Science , 1994 .

[39]  M. Herberhold,et al.  1,3-Dioxa-[3]ferrocenophane , 1993 .

[40]  Ling‐Kang Liu,et al.  Preparation and crystal structures of iron complexes syn-[(.mu.-SPh)Fe(CO)3]2, (C5H4SPh)2Fe, (C5H5)Fe(C5H4SPh), and (C5H4SPh)Fe(C5H4PPh2) , 1992 .

[41]  Sadao. Sato,et al.  Preparation and crystal structures of (1,1'-ruthenocenedithiolato-S,S',Ru)(triphenylphosphine)nickel(II) and [1,1'-metallocenedioxalato-O,O',Fe(or Ru)](triphenylphosphine)palladium(II): the metal (iron or ruthenium)-metal (palladium or nickel) dative bond , 1987 .

[42]  M. Ônishi,et al.  Syntheses and properties of 2-[(dimethylamino)methyl]-1-hydroxyferrocene and its derivatives , 1984 .

[43]  A. Nesmejanow,et al.  Synthese von Ferrocenderivaten mittels bor‐ und halogensubstituierter Ferrocene , 1960 .