Non-metallocene rare-earth organometallic derivatives: synthesis, structure and application in the catalysis of transformations of unsaturated substrates

The post-metallocene period of development of the chemistry of rare-earth organometallic compounds is analysed. The synthesis, structures and reactivities of complexes containing metal–carbon and metal–hydrogen bonds and stabilised by N-, P, and O-donor ligands are considered. The catalytic activities of these compounds in alkene polymerisation, hydroamination, hydrosilylation and hydroboration are discussed.

[1]  F. Hampel,et al.  3,3'-Bis(trisarylsilyl)-substituted binaphtholate rare earth metal catalysts for asymmetric hydroamination. , 2006, Journal of the American Chemical Society.

[2]  F. Perdih,et al.  Structure−Reactivity Relationships in Rare-Earth Metal Carboxylate-Based Binary Ziegler-Type Catalysts , 2006 .

[3]  W. Wong,et al.  Synthesis, Reactivity, and Characterization of Amine Bis(phenolate) Lanthanide Complexes and Their Application in the Polymerization of ε-Caprolactone , 2005 .

[4]  Benjamin D. Ward,et al.  A Family of Scandium and Yttrium Tris((trimethylsilyl)methyl) Complexes with Neutral N3 Donor Ligands , 2005 .

[5]  O. Eisenstein,et al.  Hydrogen for fluorine exchange in C6F6 and C6F5H by monomeric [1,3,4-(Me3C)3C5H2]2CeH: experimental and computational studies. , 2005, Journal of the American Chemical Society.

[6]  T. Marks,et al.  Organolanthanide-catalyzed synthesis of phosphine-terminated polyethylenes. Scope and mechanism. , 2005, Journal of the American Chemical Society.

[7]  Paul G. Hayes,et al.  Synthesis, Structure, and Ion Pair Dynamics of β-Diketiminato-Supported Organoscandium Contact Ion Pairs , 2005 .

[8]  Jun Wang,et al.  Alkali-metal, halide, and lewis base free monomeric alkylsamarium(III) porphyrinogen complexes of high stability , 2005 .

[9]  K. Hultzsch.  Transition Metal‐Catalyzed Asymmetric Hydroamination of Alkenes (AHA) , 2005 .

[10]  Stuart R. Dubberley,et al.  Lanthanide mono(borohydride) complexes of diamide-diamine donor ligands: novel single site catalysts for the polymerisation of methyl methacrylate. , 2005, Dalton transactions.

[11]  O. Eisenstein,et al.  Hydrogen for Fluorine Exchange in C 6 F 6 and C 6 F 5 H by Monomeric [1,3,4-(Me 3 C) 3 C 5 H 2 ] 2 CeH: Experimental and Computational Studies , 2005 .

[12]  H. Yasuda,et al.  Developments of rare earth metal catalysts for olefin polymerization , 2004 .

[13]  T. Marks,et al.  Organolanthanide-catalyzed synthesis of phosphine-terminated polyethylenes. , 2004, Journal of the American Chemical Society.

[14]  Z. Hou,et al.  Scandium half-metallocene-catalyzed syndiospecific styrene polymerization and styrene-ethylene copolymerization: unprecedented incorporation of syndiotactic styrene-styrene sequences in styrene-ethylene copolymers. , 2004, Journal of the American Chemical Society.

[15]  S. Gambarotta,et al.  Preparation of an Active Neodymium Catalyst for Regioselective Butadiene cis-Polymerization Supported by a Dianionic Modification of the 2,6-Diiminopyridine Ligand , 2004 .

[16]  M. W. Bouwkamp,et al.  One ligand fits all: cationic mono(amidinate) alkyl catalysts over the full size range of the group 3 and lanthanide metals. , 2004, Journal of the American Chemical Society.

[17]  T. Marks,et al.  Organolanthanide-catalyzed hydroamination. , 2004, Accounts of chemical research.

[18]  F. Hampel,et al.  New Yttrium Complexes Bearing Diamidoamine Ligands as Efficient and Diastereoselective Catalysts for the Intramolecular Hydroamination of Alkenes and Alkynes , 2004 .

[19]  Paul G. Hayes,et al.  Scandium-Catalyzed Intramolecular Hydroamination. Development of a Highly Active Cationic Catalyst , 2004 .

[20]  B. Hessen,et al.  Yttrium Alkyl Complexes with Triamino−Amide Ligands , 2004 .

[21]  P. Fleurat‐Lessard,et al.  β-Diketiminato scandium chemistry: Synthesis, characterization, and thermal behavior of primary amido alkyl derivatives , 2004 .

[22]  B. Hessen,et al.  Neutral and cationic alkyl and alkynyl complexes of lanthanum: Synthesis, stability, and cis-selective linear alkyne dimerization , 2004 .

[23]  T. Marks,et al.  C2-symmetric bis(oxazolinato)lanthanide catalysts for enantioselective intramolecular hydroamination/cyclization. , 2003, Journal of the American Chemical Society.

[24]  A. Mortreux,et al.  Neodymium alk(aryl)oxides-dialkylmagnesium systems for butadiene polymerization and copolymerization with styrene and glycidyl methacrylate , 2003 .

[25]  L. Toupet,et al.  Synthesis, structure and reactivity of new yttrium bis(dimethylsilyl)amido and bis(trimethylsilyl)methyl complexes of a tetradentate bis(phenoxide) ligand , 2003 .

[26]  Yingming Yao,et al.  Synthesis, crystal structure of bis(arylamido)lanthanide methyl complexes and their catalytic behavior for the polymerization of methyl methacrylate , 2003 .

[27]  Craig L. Reeder,et al.  Highly Isospecific Polymerization of Methyl Methacrylate with a Bis(pyrrolylaldiminato)samarium Hydrocarbyl Complex , 2003 .

[28]  G. Yap,et al.  Donor-functionalized lanthanide terphenyl complexes: Synthesis and structural characterization of 2,6-di(o-anisol)phenyl compounds of ytterbium, yttrium, and samarium. , 2003, Inorganic chemistry.

[29]  Paul G. Hayes,et al.  Cationic organoscandium beta-diketiminato chemistry: arene exchange kinetics in solvent separated ion pairs. , 2003, Journal of the American Chemical Society.

[30]  Paul G. Hayes,et al.  A New Chelating Anilido-Imine Donor Related to β-Diketiminato Ligands for Stabilization of Organoyttrium Cations , 2003 .

[31]  Frauke Pohlki,et al.  The catalytic hydroamination of alkynes. , 2003, Chemical Society reviews.

[32]  E. Herdtweck,et al.  Organo-Rare-Earth Complexes Supported by Chelating Diamide Ligands , 2003 .

[33]  E. Herdtweck,et al.  Reactivity of Trimethylaluminum with Lanthanide Aryloxides: Adduct and Tetramethylaluminate Formation , 2003 .

[34]  A. Lara‐Sánchez,et al.  Synthesis, structure and catalytic activity of new iminophenolato complexes of scandium and yttrium , 2002 .

[35]  W. Piers.  Non-cyclopentadienyl ancillaries in organogroup 3 metal chemistry: a fine balance in ligand design , 2002 .

[36]  Yingming Yao,et al.  [(SiMe3)2NC(NiPr)2]2Ln(μ-Me)2Li(TMEDA) (Ln = Nd, Yb) as Effective Single-Component Initiators for Styrene Polymerization , 2002 .

[37]  F. Perdih,et al.  Rare-Earth Ziegler−Natta Catalysts: Carboxylate−Alkyl Interchange , 2002 .

[38]  Z. Hou,et al.  Recent developments in organolanthanide polymerization catalysts , 2002 .

[39]  R. McDonald,et al.  Organometallic complexes of scandium and yttrium supported by a bulky salicylaldimine ligand , 2002 .

[40]  F. Edelmann,et al.  Synthesis and structural chemistry of non-cyclopentadienyl organolanthanide complexes. , 2002, Chemical reviews.

[41]  A. Mortreux,et al.  Homogeneous and heterogeneous alkyl-alkoxo-lanthanide type catalysts for polymerization and block-copolymerization of ethylene and methyl methacrylate , 2002 .

[42]  S. Arndt,et al.  Mono(cyclopentadienyl) complexes of the rare-earth metals. , 2002, Chemical reviews.

[43]  G. Molander,et al.  Lanthanocene catalysts in selective organic synthesis. , 2002, Chemical reviews.

[44]  Benjamin D. Ward,et al.  New N- and O-donor ligand environments in organoscandium chemistry , 2002 .

[45]  J. Takats,et al.  [(Tpt-Bu,Me)Yb(μ-H)]2: a fecund precursor to a host of divalent, hydrotris(pyrazolyl)borate supported f-element complexes , 2002 .

[46]  Paul G. Hayes,et al.  Cationic scandium methyl complexes supported by a beta-diketiminato ("Nacnac") ligand framework. , 2002, Journal of the American Chemical Society.

[47]  B. Scott,et al.  Observation of a Significantly Reduced 1JC-H Coupling Constant in an Agostic f-Element Complex: X-ray Crystal Structure of (ArO)Sm[(μ-OAr)(μ-Me)AlMe2]2 (Ar = 2,6-i-Pr2C6H3) , 2002 .

[48]  B. Driessen-Hölscher,et al.  Recent Developments in Transition Metal Catalyzed Intermolecular Hydroamination Reactions-A Breakthrough? , 2001, Angewandte Chemie.

[49]  Paul G. Hayes,et al.  Dialkylscandium Complexes Supported by β-Diketiminato Ligands: Synthesis, Characterization, and Thermal Stability of a New Family of Organoscandium Complexes , 2001 .

[50]  P. Bailey,et al.  The coordination chemistry of guanidines and guanidinates , 2001 .

[51]  Francesca M. Kerton,et al.  Carbon−Carbon Bond Formation Using Yttrium(III) and the Lanthanide Elements , 2001 .

[52]  J. H. Teuben,et al.  Yttrium alkyl complex with a linked bis(amidinate) ancillary ligand , 2001 .

[53]  D. Richeson,et al.  Tetrasubstituted Guanidinate Anions as Supporting Ligands in Organoyttrium Chemistry , 2001 .

[54]  R. McDonald,et al.  Bimolecular extrusion of TeR2 from beta-diketiminato supported scandium bis-tellurolates. , 2000, Chemistry.

[55]  J. H. Teuben,et al.  Yttrium alkyl and benzyl complexes with amino-amidinate monoanionic ancillary ligands , 2000 .

[56]  P. Roesky.  Bridged aminotroponiminate complexes of lutetium , 2000 .

[57]  T. Marks,et al.  Organolanthanide-Catalyzed Intramolecular Hydrophosphination/Cyclization of Phosphinoalkenes and Phosphinoalkynes , 2000 .

[58]  G. Yap,et al.  Dinuclear Complexes of Di-, Tri-, and Mixed-Valent Samarium Supported by the Calix-tetrapyrrole Ligand , 2000 .

[59]  G. Yap,et al.  Samarium Hydride, Methyl, and Vinyl Complexes Supported by Calix-tetrapyrrole Ring Macrocycle. Thermal Decomposition to Samarium(II) , 2000 .

[60]  T. Tilley,et al.  Hydrosilylation Catalysis by C2-Symmetric Bis(silylamido) Complexes of Yttrium , 1999 .

[61]  W. Piers,et al.  Synthesis of dialkylscandium complexes supported by β-diketiminato ligands and activation with tris (pentafluorophenyl)borane , 1999 .

[62]  T. Tilley,et al.  Yttrium Complexes of the Chelating, C2-Symmetric, Bis(silylamido)biphenyl Ligand [DADMB]2- (={[6,6‘-Me2-(C6H3)2](2,2‘-NSiMe2tBu)2}2-) , 1999 .

[63]  W. M. Davis,et al.  Synthesis of yttrium complexes that contain the [NON]{sup 2-} ligand, [(t-Bu-d{sub 6}-N-o-C{sub 6}H{sub 4}){sub 2}O]{sup 2-} , 1998 .

[64]  J. Ziller,et al.  SYNTHESIS, STRUCTURE, AND REACTIVITY OF CYCLOPENTADIENYL-FREE TRIMETHYLSILYLMETHYL YTTRIUM DI-TERT-BUTYLPHENOXIDE COMPLEXES , 1998 .

[65]  G. Yap,et al.  N-Substituted Guanidinate Anions as Ancillary Ligands in Organolanthanide Chemistry. Synthesis and Characterization of {CyNC[N(SiMe3)2]NCy}2SmCH(SiMe3)2 , 1998 .

[66]  M. Beller,et al.  Metal-Initiated Amination of Alkenes and Alkynes. , 1998, Chemical reviews.

[67]  H. Yasuda.  Organo-rare-earth-metal initiated living polymerizations of polar and nonpolar monomers , 2002 .

[68]  R. Duchateau,et al.  Synthesis and reactivity of bis(alkoxysilylamido)yttrium eta(2)-pyridyl and eta(2)-alpha-picolyl compounds , 1997 .

[69]  M. Ephritikhine.  Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements. , 1997, Chemical reviews.

[70]  J. Love,et al.  Arene coordination to yttrium(III) via carbon-carbon bond formation , 1997 .

[71]  I. Beletskaya,et al.  Reactivity of lanthanide and yttrium hydrides and hydrocarbyls toward organosilicon hydrides and related compounds , 1997 .

[72]  T. Tuinstra,et al.  Alternatives for Cyclopentadienyl Ligands in Organoyttrium Chemistry: Bis(N,O-bis(tert-butyl)(alkoxydimethylsilyl)amido)yttrium Compounds , 1997 .

[73]  F. Einstein,et al.  Synthesis, X-ray Crystal Structure, and Reactivity of Y(MAC)(CH2SiMe3)2 (MAC = Deprotonated aza-18-crown-6) , 1997 .

[74]  W. Schaefer,et al.  HIGHLY ELECTRON DEFICIENT GROUP 3 ORGANOMETALLIC COMPLEXES BASED ON THE 1,4,7-TRIMETHYL-1,4,7-TRIAZACYCLONONANE LIGAND SYSTEM , 1997 .

[75]  D. Long,et al.  A Catalytic System for Ethylene Polymerization Based on Group III and Lanthanide Complexes of Tris(pyrazolyl)borate Ligands , 1996 .

[76]  J. Ziller,et al.  Utility of Arylamido Ligands in Yttrium and Lanthanide Chemistry(1). , 1996, Inorganic chemistry.

[77]  M. D. Fryzuk,et al.  Synthesis and Characterization of the Five-Coordinate Scandium Dialkyl Complexes ScR2[N(SiMe2CH2PPri2)2] (R = Me, Et, CH2SiMe3) , 1996 .

[78]  C. T. Wee,et al.  Insertion and C−H Bond Activation of Unsaturated Substrates by Bis(benzamidinato)yttrium Alkyl, [PhC(NSiMe3)2]2YR (R = CH2Ph·THF, CH(SiMe3)2), and Hydrido, {[PhC(NSiMe3)2]2Y(μ-H)}2, Compounds , 1996 .

[79]  C. T. Wee,et al.  Ancillary Ligand Effects in Organoyttrium Chemistry: Synthesis, Characterization, and Electronic Structure of Bis(benzamidinato)yttrium Compounds , 1996 .

[80]  J. Ziller,et al.  Synthetic and Structural Studies of the Cyclopentadienyl-Free Yttrium Alkyl Alkoxide and Aryloxide Complexes [(Me3Si)2CH]2Y(μ-OCMe3)2Li(THF) and [Me3SiCH2]2Y(OC6H3tBu2-2,6)(THF)2 , 1996 .

[81]  J. Arnold,et al.  PREPARATION OF SCANDIUM COMPLEXES WITH BENZAMIDINATE LIGANDS : SYNTHESIS AND REACTIVITY OF ALKYL AND HYDRIDO DERIVATIVES , 1996 .

[82]  G. W. Bushnell,et al.  Reversible Yttrium Alkynide Coupling Supported by DAC (Deprotonated 4,13-Diaza-18-crown-6) Ligation , 1995 .

[83]  J. Ziller,et al.  HETEROPOLYAGOSTIC INTERACTIONS IN LANTHANIDE(III) DIISOPROPYLAMIDO COMPLEXES , 1995 .

[84]  L. Esser,et al.  Synthesis, Structure, and Reactivity of Organometallic .pi.-Complexes of the Rare Earths in the Oxidation State Ln3+ with Aromatic Ligands , 1995 .

[85]  R. Duchateau,et al.  Early transition metal catalyzed-hydroboration of alkenes , 1995 .

[86]  H. Schumann,et al.  Metallorganische Verbindungen der Lanthanoide. 88. Monomere Lanthanoid(III)‐amide: Synthese und Röntgenstrukturanalyse von [Nd{N(C6H5)(SiMe3)}3(THF)], [Li(THF)2(μ‐Cl)2Nd{N(C6H3Me2‐2,6)(SiMe3)}2(THF)] und [ClNd{N(C6H3‐iso‐Pr2‐2,6)(SiMe3)}2(THF)] , 1995 .

[87]  G. W. Bushnell,et al.  Synthesis, X-ray Crystal Structure, and Thermal Stability of Y[DAC][CH2SiMe3] (DAC = Deprotonated 4,13-Diaza-18-crown-6) , 1995 .

[88]  G. W. Bushnell,et al.  Syntheses and Fluxional Behavior of Yttrium Complexes Containing the Bulky Arylsiloxide OSitBuAr2 [Ar = o-C6H4(CH2NMe2)] and the X-ray Crystal Structure of Y[OSitBuAr2][N(SiMe3)2]2 , 1994 .

[89]  J. Huffman,et al.  Samarium alkyl-aryloxide complex containing a trigonal bipyramidal carbon atom. X-ray structure of [Li(THF)][sub 2][Sm(O-2,6-i-Pr[sub 2]C[sub 6]H[sub 3])[sub 3] CH[sub 2]SiMe[sub 3][sub 2]] , 1994 .

[90]  R. Rogers,et al.  Application of the Sterically Demanding Hydrotris(3-tert-butyl-5-methylpyrazolyl)borate Ligand to Ln(II) Chemistry: Synthesis of a New Class of Mixed-Ligand Yb(II) Complexes , 1994 .

[91]  F. Arnaud-Neu.  Solution chemistry of lanthanide macrocyclic complexes , 1994 .

[92]  F. Hollander,et al.  Preparation, characterization, and reactivity of scandium octaethylporphyrin complexes. X-ray crystal structures of (OEP)ScCH3, (OEP)ScCH(SiMe3)2, (OEP)Sc(.eta.5-C9H7), and [(OEP)Sc]2(.mu.-OH)2 , 1993 .

[93]  H. J. Heeres,et al.  Reversible carbon-carbon bond formation in organolanthanide systems. Preparation and properties of lanthanide acetylides [Cp*{sub 2}LnC{triple_bond}CR]{sub n} and their rearrangement products [Cp*{sub 2}Ln]{sub 2}({mu}-{eta}{sup 2}:{eta}{sup 2}-RC{sub 4}R) (Ln = La, Ce, R = Alkyl) , 1993 .

[94]  C. T. Wee,et al.  BIS(TRIMETHYLSILYL)BENZAMIDINATE - A PROMISING SPECTATOR LIGAND IN ORGANOYTTRIUM CHEMISTRY - SYNTHESIS AND REACTIVITY OF ([C6H5C(NSIME3)2]2Y-MU-R)2(R = H, CCH) AND X-RAY STRUCTURE OF ([C6H5C(NSIME3)2]2Y-MU-CCH)2 , 1993 .

[95]  T. Boyle,et al.  Reactivity of Y3(OR)7Cl2(THF)2 with organoaluminum reagents: formation of the yttrium-aluminum complexes Y(OR)3(AlMe3)3, Y(OR)3(AlMe3)2(THF), and Y(OR)3(AlMe2)Cl(THF)2 and the halides YCl3(DME)2 and YCl3(THF)3Y3(OR)7O (R = CMe3) , 1993 .

[96]  T. Marks,et al.  Organolanthanide-catalyzed hydroboration of olefins , 1992 .

[97]  C. Schaverien.  Cationic lanthanide alkyl complexes. Evidence for an unprecedented tetraphenylborate coordination mode in La(C5Me5){CH(SiMe3)2}BPh4 , 1992 .

[98]  M. D. Fryzuk,et al.  Mono(amido-diphosphine) complexes of yttrium: Synthesis and X-ray crystal structure of (Y({eta}{sup 3}-C{sub 3}H{sub 5})[N(SiMe{sub 2}CH{sub 2}PMe{sub 2}){sub 2}]){sub 2}({mu}-Cl){sub 2} , 1992 .

[99]  V. Conticello,et al.  Chiral organolanthanide complexes for enantioselective olefin hydrogenation , 1992 .

[100]  G. Soloveichik,et al.  Unsolvated lanthanidocene hydrides and borohydrides. X-Ray crystal structure of [(η5-C5H3tBu2)2Ln(μ-H)]2 (Ln = Ce, Sm) , 1992 .

[101]  A. Orpen,et al.  Chemistry of (octaethylporphyrinato)lutetium and -yttrium complexes: synthesis and reactivity of (OEP)MX derivatives and the selective activation of O2 by (OEP)Y(.mu.-Me)2AlMe2 , 1991 .

[102]  M. D. Fryzuk,et al.  Phosphine complexes of yttrium, lanthanum, and lutetium. Synthesis, thermolysis, and fluxional behavior of the hydrocarbyl derivatives MR[N(SiMe2CH2PMe2)2]2. X-ray crystal structure of [cyclic] Y[N(SiMe2CHPMe2)(SiMe2CH2PMe2)][N(SiMe2CH2PMe2)2] , 1991 .

[103]  M. D. Fryzuk,et al.  Complexes of groups 3, 4, the lanthanides and the actinides containing neutral phosphorus donor ligands , 1990 .

[104]  T. Marks,et al.  Manipulation of organolanthanide coordinative unsaturation. Synthesis, structures, structural dynamics, comparative reactivity, and comparative thermochemistry of dinuclear .mu.-hydrides and .mu.-alkyls with [.mu.-R2Si(Me4C5)(C5H4)]2 supporting ligation , 1990 .

[105]  M. D. Fryzuk,et al.  Phosphine complexes of yttrium(III). Synthesis, reactivity, and fluxional behavior of YCl[N(SiMe2CH2PMe2)2]2 , 1988 .

[106]  Olga Kennard,et al.  Tables of bond lengths determined by X-ray and neutron diffraction. Part 1. Bond lengths in organic compounds , 1987 .

[107]  T. Marks,et al.  Highly reactive organolanthanides. A mechanistic study of catalytic olefin hydrogenation by bis(pentamethylcyclopentadienyl) and related 4f complexes , 1986 .

[108]  P. N. Swepston,et al.  Highly reactive organolanthanides. Systematic routes to and olefin chemistry of early and late bis(pentamethylcyclopentadienyl) 4f hydrocarbyl and hydride complexes , 1985 .

[109]  T. Marks,et al.  Highly reactive organolanthanides. Synthesis, chemistry, and structures of 4f hydrocarbyls and hydrides with chelating bis(polymethylcyclopentadienyl) ligands , 1985 .

[110]  I. Bloom,et al.  Organolanthanide hydride chemistry. 3. Reactivity of low-valent samarium with unsaturated hydrocarbons leading to a structurally characterized samarium hydride complex , 1983 .

[111]  R. D. Shannon.  Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .