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Crowded Diphosphinomethane Ligands In Catalysis: [(R2PCH2PR′2-κ2P)-NiR″]+ Cations For Ethylene Polymerization Without Activators

M. Schultz, Frank Eisentraeger, Christian T. Regius, F. Rominger, Patrick Hanno-Igels, P. Jakob, I. Gruber, P. Hofmann
Published 2012 · Chemistry

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The preparation of a series of nickel dichloride complexes with bulky diphosphinomethane chelate ligands R2PCH2PR′2 is reported. Reaction with the appropriate Grignard reagent leads to the corresponding dimethyl and dibenzyl complexes. Cationic monomethyl and mono-η3-benzyl complexes are generated from these dialkyl complexes by protonation with [H(OEt2)2]+[B(3,5-(CF3)2C6H3)4]−, while the complex [(dtbpm κ2P)Ni(η3-CH(CH2Ph)Ph]+[B(3,5-(CF3)2C6H3)4]−is obtained from protonation of the Ni(0) olefin complex (dtbpm-κ2P)N(η2-trans-stilbene). Crystal structures of examples of dichlorides, dimethyl, dibenzyl, cationic methyl, and cationic η3-benzyl complexes are reported. Solutions of the cations polymerize ethylene under mild conditions and without the necessity of an activating agent, to form polyethylene having high molecular weights and low degrees of chain branching. In comparison to the Ni methyl cations, the η3-benzyl cation complexes are more stable and somewhat less active but still very efficient in C2H4 polymerization. The effect on the resulting polyethylene of varying the substituents R, R′ on the phosphine ligand has been examined, and a clear trend for longer chain PE with less branching in the presence of more bulky substituents on the diphosphine has been found. Density functional calculations have been used to examine the rapid suprafacial η3 to η3 haptotropic shift processes of the[(R2PCH2PR′2)Ni] fragment and the η3−η1 change of the coordination mode of the benzyl group required for polymerization in those cations.
This paper references
10.1021/JA962860E
A Density Functional Study of Nickel(II) Diimide Catalyzed Polymerization of Ethylene
Liqun Deng (1997)
10.1021/OM030655J
Synthesis, Structure, and Reactivity of Cationic Ruthenium(II) Carbene Complexes with Bulky Chelating Bisphosphines: Design of Highly Active Ring Opening Metathesis Polymerization (ROMP) Catalysts
M. A. Volland (2004)
10.1021/OM010705P
Nickel Ethylene Polymerization Catalysts Based on Phosphorus Ligands
N. Cooley (2001)
10.1039/A801933I
Novel olefin polymerization catalysts based on iron and cobalt
G. Britovsek (1998)
10.1021/JA970226A
The Role of Bulky Substituents in Brookhart-Type Ni(II) Diimine Catalyzed Olefin Polymerization: A Combined Density Functional Theory and Molecular Mechanics Study
Liqun Deng (1997)
10.1039/C001190H
Directing role of functional groups in selective generation of C–H⋯π interactions: In situ cryo-crystallographic studies on benzyl derivatives
S. K. Nayak (2010)
10.1002/(SICI)1521-3773(19990215)38:4<428::AID-ANIE428>3.0.CO;2-3
The Search for New-Generation Olefin Polymerization Catalysts: Life beyond Metallocenes.
G. Britovsek (1999)
10.1016/0022-328X(94)05173-9
Bis(di-t-butylphosphino)methane complexes of rhodium: homogeneous alkyne hydrosilylation by catalyst-dependent alkyne insertion into RhSi or RhH bonds. Molecular structures of the dimer [(dtbpm)RhCl]2 and of the silyl complex (dtbpm) Rh[Si(OEt)3](PMe3)☆
P. Hofmann (1995)
10.1021/OM010111M
Formation of Phenylene Oligomers Using Platinum−Phosphine Complexes
N. Simhai (2001)
10.1021/MA061547M
13C NMR Analysis of α-Olefin Enchainment in Poly(α-olefins) Produced with Nickel and Palladium α-Diimine Catalysts
E. Mccord (2007)
10.1007/S10562-010-0416-Y
Bis(Pyrazolyl)Pyridine Late Transition Metal Complexes as Single-Site Catalysts for Ethylene Polymerization to Highly Linear Polyethylene
H. S. Abbo (2010)
10.1021/JA962516H
Living Polymerization of α-Olefins Using NiII−α-Diimine Catalysts. Synthesis of New Block Polymers Based on α-Olefins
Christopher Moore Killian (1996)
10.1021/OM00039A024
.eta.2-(C,O) Ketene coordination at nickel(O). Synthesis, bonding, and molecular structure of (dtbpm)Ni[.eta.2-(C,O)-Ph2C2O] [dtbpm = bis(di-tert-butylphosphino)methane]
P. Hofmann (1992)
10.1021/JA953247I
Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium(II) Catalysts
L. Johnson (1996)
10.1021/cr900079r
Coordination-insertion copolymerization of fundamental polar monomers.
Akifumi Nakamura (2009)
10.1016/J.MOLCATA.2004.10.056
Catalytic polymerisation of ethylene with tris(pyrazolyl)borate complexes of late transition metals
R. Santi (2005)
10.1021/JA964144I
Mechanistic Studies of the Palladium-Catalyzed Copolymerization of Ethylene and α-Olefins with Methyl Acrylate
S. Mecking (1998)
10.1016/S0020-1693(02)01293-8
The role of bulky substituents in the polymerization of ethylene using late transition metal catalysts: a comparative study of nickel and iron catalyst systems
G. Britovsek (2003)
10.1021/OM00059A071
[(3,5-(CF3)2C6H3)4B]-[H(OEt2)2]+: a convenient reagent for generation and stabilization of cationic, highly electrophilic organometallic complexes
M. Brookhart (1992)
10.1021/OM971137+
The Dynamics of the β-Agostic Isopropyl Complex (ArNC(R)−C(R)NAr)Pd(CH(CH2-μ-H)(CH3))+BAr4‘- (Ar = 2,6-C6H3(i-Pr)2): Evidence for In-Place Rotation versus Dissociation of the Agostic Methyl Group
D. J. Tempel (1998)
10.1524/ZKRI.1996.211.1.60
Crystal structure of cis-chloromethyl[η2-bis(di-tert-butylphosphino)-methane]nickel(II), ((C4H9)2P)2CH2NiCH3Cl
R. Ficker (1996)
10.1039/B210114A
Sterically crowded diphosphinomethane ligands: molecular structures, UV-photoelectron spectroscopy and a convenient general synthesis of tBu2PCH2PtBu2 and related species
Frank Eisentraeger (2003)
10.1002/ANIE.200353226
Cyclophane-based highly active late-transition-metal catalysts for ethylene polymerization.
D. Camacho (2004)
10.1021/OM0008023
Cationic Four- and Five-Coordinate Nickel(II) Complexes: Insights into the Nickel(II)-Catalyzed Copolymerization of Ethylene and Carbon Monoxide
C. S. Shultz (2001)
10.1021/CR9804644
Late-metal catalysts for ethylene homo- and copolymerization.
S. D. Ittel (2000)
10.1021/OM000705+
Density Functional Study of Ethylene Polymerization Catalyzed by a Zirconium Non-Cyclopentadienyl Complex, L2ZrCH3+. Effects of Ligands and Bulky Substituents
S. Vyboishchikov (2001)
10.1016/0022-328X(91)80176-K
Efficient palladium catalysts for the copolymerization of carbon monoxide with olefins to produce perfectly alternating polyketones
E. Drent (1991)
10.1021/OM000872+
Nickel Indenyl Complexes as Catalysts for the Dimerization and Polymerization of Ethylene
†. Dubois (2001)
10.1021/OM0206305
Polymerization of Ethylene with Cationic Palladium and Nickel Catalysts Containing Bulky Nonenolizable Imine−Phosphine Ligands
O. Daugulis (2002)
10.1021/OM0494014
Diphosphine Complexes of Nickel(II) Are Efficient Catalysts for the Polymerization and Oligomerization of Ethylene: Steric Activation and Ligand Backbone Effects
James N. L. Dennett (2004)
10.1002/ANIE.197804661
Novel Coordination of (Benzoylmethylene)triphenylphosphorane in a Nickel Oligomerization Catalyst
W. Keim (1978)
10.1016/J.CCR.2005.06.002
Polymerized metallocene catalysts and late transition metal catalysts for ethylene polymerization
Jun Zhang (2006)
10.1021/JA0056062
Facile reductive elimination of ethane from strained dimethylpalladium(II) complexes.
S. M. Reid (2001)
10.1002/CBER.19921250319
Room-temperature C-F bond activation of hexafluorobenzene by a tailor-made Pt(0) intermediate, [(dtbpm)Pt(0)]
P. Hofmann (1992)
10.1021/JA992689H
Toward an alkene hydroamination catalyst: static and dynamic ab initio DFT studies
H. Senn (2000)
10.1016/J.JORGANCHEM.2003.12.007
Cationic η3-benzyl nickel compounds with diphosphine ligands as catalyst precursors for ethylene oligomerization/polymerization: influence of the diphosphine bite angle
I. Albers (2004)
10.1021/JA004191H
α-Iminocarboxamidato−Nickel(II) Ethylene Polymerization Catalysts
B. Lee (2001)
10.1002/ANIE.199008801
Novel Platinum Complexes Enable Selective C‐H and C‐Si Activation of Tetramethylsilane at Room Temperature
P. Hofmann (1990)
10.1021/OM010503T
Reversible Carbon−Carbon Double Bond Cleavage of a Ketene Ligand at a Single Iridium(I) Center: A Theoretical Study§
H. Urtel (2001)
10.1016/S0020-1693(99)00460-0
Synthesis and characterization of a series of novel nickel(II)/nickel(I) complexes. Crystal structures of [NiCl2(dcpm)], [Ni(dcpm)2](NO3)2·2EtOH, [Ni2Cl2(μ-dcpm)2(μ-H)] and [Ni2(μ-PCy2)2(PCy2Me)2]; dcpm=bis(dicyclohexylphosphino)methane
C. E. Kriley (2000)
10.1002/CBER.19921250212
Bis(di‐tert‐butylphosphanyl)methan‐Komplexe des Rhodiums: Geometrie, Elektronenstruktur und Derivate des 14‐Elektronenteilchens [Rh(dtbpm)Cl]. Molekülstruktur von Rh(dtbpm)Cl(PMe3)
P. Hofmann (1992)
10.1002/jcc.21392
How the choice of a computational model could rule the chemical interpretation: The Ni(II) catalyzed ethylene dimerization as a case study
V. Tognetti (2010)
10.1021/MA971639Z
Addition Polymerization of Cyclopentene with Nickel and Palladium Catalysts
S. Mclain (1998)
10.1021/JA0160896
Four- and five-coordinate CO insertion mechanisms in d(8)-nickel(II) complexes.
C. Shultz (2001)
10.1021/OM030388H
Polymerization and oligomerization of ethylene by cationic nickel(II) and palladium(II) complexes containing bidentate phenacyldiarylphosphine ligands
Jon M. Malinoski (2003)
10.1016/J.PROGPOLYMSCI.2006.11.001
Living alkene polymerization : New methods for the precision synthesis of polyolefins
Gregory J. Domski (2007)
10.1021/MA991234+
Synthesis of branched polyethylene using (α-diimine)nickel(II) catalysts : influence of temperature, ethylene pressure, and ligand structure on polymer properties
Derek P Gates (2000)
10.1021/JA991931H
Low-Temperature Spectroscopic Observation of Chain Growth and Migratory Insertion Barriers in (α-Diimine)Ni(II) Olefin Polymerization Catalysts
S. A. Svejda (1999)
10.1002/ANGE.19901020822
Neuartige Platinkomplexe ermöglichen selektive C‐H‐ und C‐Si‐Aktivierung von Tetramethylsilan bei Raumtemperatur
P. Hofmann (1990)
10.1021/IE50026A027
Koenig Potash Bulb
W. Koenig (1911)
10.1524/ZKRI.1996.211.1.58
Crystal structure of [η2-bis(trimethylsilyl)acetylene][η2-bis(di-tert-butylphosphino)methane]nickel(0), ((CH3)3Si)2C2((C4H9)2P)2CH2Ni
R. Ficker (1996)
10.1021/IC991173W
A trigonal planar mu 3-fluorido coinage metal complex from a dicationic (diphosphinomethane)copper(I) dimer: syntheses, structures, and bonding.
B. Straub (2000)
10.1021/JA021071W
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.
Mark D. Leatherman (2003)
10.1021/JA9628314
A Density Functional Study of the Mechanism of the Diimine−Nickel-Catalyzed Ethylene Polymerization Reaction
D. Musaev (1997)
10.1002/MARC.200350009
η3-Benzyl-nickel-diimine complex: Synthesis and catalytic properties in ethylene polymerization
V. Fassina (2003)
10.1021/JA00128A054
New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and .alpha.-Olefins
L. Johnson (1995)
10.1021/OM0201516
Ethylene Polymerization and Ethylene/Methyl 10-Undecenoate Copolymerization Using Nickel(II) and Palladium(II) Complexes Derived from a Bulky P,O Chelating Ligand
Weijun Liu (2002)
10.1524/ZKRI.1996.211.1.62
Crystal structure of dicarbonyl[η2-bis(di-tert-butylphosphino)-methane]nickel(0), ((C4H9)2P)2CH2Ni(CO)2
R. Ficker (1996)
10.1021/OM100413M
Neutral cis-Alkyl Olefin Rhodium(I) Complexes: Models of Intermediates in Late Transition Metal Olefin Polymerization with Surprising Structure†
H. Urtel (2010)



This paper is referenced by
10.1021/OM400711D
Bis(diisopropylphosphinomethyl)amine Nickel(II) and Nickel(0) Complexes: Coordination Chemistry, Reactivity, and Catalytic Decarbonylative C–H Arylation of Benzoxazole
Achim Kruckenberg (2013)
10.1002/chem.201504483
Methyl Complexes of the Transition Metals.
J. Campos (2016)
10.1002/AOC.3183
Vinyl polymerization of norbornene catalyzed by 2‐Py‐amidine Ni(II) complex/methylaluminoxane systems
Yong-Ping Niu (2014)
10.1002/asia.201300687
Solvent-dependent reversible ligand exchange in nickel complexes of a monosulfide bis(diphenylphosphino)(N-thioether)amine.
A. Ghisolfi (2013)
10.1038/s41467-019-08309-8
A highly active Ni(II)-triadamantylphosphine catalyst for ultrahigh-molecular-weight polyethylene synthesis
Andrew L. Kocen (2019)
10.1021/ACS.ORGANOMET.5B00396
Syntheses and Structures of [CH2(NCnH2n)2]Mo(CO)4 (n = 4,5) Complexes with Bis(cycloamine) Ligands Easily Prepared from CH2Cl2
Samuel J. Kyran (2015)
10.1016/J.ICA.2016.07.048
Nickel(II) and nickel(0) complexes of bis(diisopropylphosphino)amine: Synthesis, structure, and electrochemical activity
D. Dickie (2016)
10.1021/ACS.ORGANOMET.6B00850
Oligomerization of Ethylene Using a Diphosphine Palladium Catalyst
David Bézier (2017)
10.1039/c7dt03395h
Catalytic applications of small bite-angle diphosphorus ligands with single-atom linkers.
S. Mansell (2017)
10.1021/OM300963T
Transition Metal Complexes of Bulky, Electron-Rich N-Phosphanyl-Substituted N-Heterocyclic Carbenes (NHCP Ligands). Small Bite Angle Four-Membered (κ-C,κ-P) Chelate Structures
Philipp Nägele (2013)
10.1016/J.JORGANCHEM.2014.04.008
Comparative study of electronic and steric properties of bulky, electron-rich bisphosphinoethane, bis-NHC and phosphino-NHC chelating ligands in analogous rhodium(I) and iridium(I) COD and carbonyl complexes
M. Brill (2015)
10.1002/9783527673278.CH10
NHCP Ligands for Catalysis
P. Hofmann (2014)
10.1021/acs.inorgchem.5b02889
Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies.
C. Fliedel (2016)
10.1021/OM500141K
Combined Experimental and Theoretical Study of Bis(diphenylphosphino)(N-thioether)amine-Type Ligands in Nickel(II) Complexes for Catalytic Ethylene Oligomerization
A. Ghisolfi (2014)
10.1016/J.INOCHE.2016.10.032
Three transition metal cluster-based coordination polymers based on 1,4-naphthalenedicarboxylate and pyridine ligands
Guo-dong Zou (2016)
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