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Title: The Nature of Secondary Interactions at Electrophilic Metal Sites of Molecular and Silica-Supported Organolutetium Complexes from Solid-State NMR Spectroscopy

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b00071· OSTI ID:1482511
 [1];  [1];  [2];  [2];  [2];  [3];  [3];  [4];  [1];  [5]
  1. Federal Inst. of Technology, Zurich (Switzerland). Dept. of Chemistry and Applied Biosciences
  2. Univ. de Lyon, Villeurbanne (France). Centre de RMN à Très Hauts Champs
  3. Univ. de Toulouse (France)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  5. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
+ Show Author Affiliations

Lu[CH(SiMe3)2]3 reacts with [SiO2-700] to give [(≡SiO)Lu[CH(SiMe3)2]2] and CH2(SiMe3)2. [(≡SiO)Lu[CH(SiMe3)2]2] is characterized by solid-state NMR and EXAFS spectroscopy, which show that secondary Lu···C and Lu···O interactions, involving a γ-CH3 and a siloxane bridge, are present. From X-ray crystallographic analysis, the molecular analogues Lu[CH(SiMe3)2]3-x[O-2,6-tBu-C6H3]x (x = 0-2) also have secondary Lu···C interactions. The 1H NMR spectrum of Lu[CH(SiMe3)2]3 shows that the -SiMe3 groups are equivalent to -125°C and inequivalent below that temperature, δ‡(Tc= 148 K)= 7.1 kcal mol-1. Both -SiMe3 groups in Lu[CH(SiMe3)2]3 have 1JCH = 117 ± 1 Hz at -140°C. The solid-state 13C CPMAS NMR spectrum at 20°C shows three chemically inequivalent resonances in the area ratio of 4:1:1 (12:3:3); the J-resolved spectra for each resonance give 1JCH = 117 ± 2 Hz. The 29Si CPMAS NMR spectrum shows two chemically inequivalent resonances with different values of chemical shift anisotropy. Similar observations are obtained for Lu[CH(SiMe3)2]3-x[O-2,6-tBu-C6H3]x (x = 1 and 2). The spectroscopic data point to short Lu···Cγ contacts corresponding to 3c-2e Lu···Cγ-Siβ interactions, which are supported by DFT calculations. Calculated natural bond orbital (NBO) charges show that Cγ carries a negative charge, while Lu, Hγ, and Siβ carry positive charges; as the number of O-based ligands increases so does the positive charge at Lu, which in turns shortens the Lu···Cγ distance. Finally, the change in NBO charges and the resulting changes in the spectroscopic and crystallographic properties show how ligands and surface-support sites rearrange to accommodate these changes, consistent with Pauling's electroneutrality concept.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1482511
Journal Information:
Journal of the American Chemical Society, Vol. 138, Issue 11; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 27 works
Citation information provided by
Web of Science

References (83)

Carbonhydrogen-transition metal bonds journal July 1983
Agostic interactions in transition metal compounds journal April 2007
Precise Control of Polyolefin Stereochemistry Using Single-Site Metal Catalysts journal April 2000
α-Agostic Interactions and Olefin Insertion in Metallocene Polymerization Catalysts journal January 1996
Stereospecific Olefin Polymerization with Chiral Metallocene Catalysts journal June 1995
Late-Metal Catalysts for Ethylene Homo- and Copolymerization journal April 2000
Rotational isomers of molybdenum(VI) alkylidene complexes and cis/trans polymer structure: investigations in ring-opening metathesis polymerization journal December 1993
Synthesis of Alternating trans -AB Copolymers through Ring-Opening Metathesis Polymerization Initiated by Molybdenum Alkylidenes journal February 2015
Formation of Alternating trans - A - alt - B Copolymers through Ring-Opening Metathesis Polymerization Initiated by Molybdenum Imido Alkylidene Complexes journal July 2015
Monoadducts of imido alkylidene complexes, syn and anti rotamers, and alkylidene ligand rotation journal June 1991
Recent Advances in High Oxidation State Mo and W Imido Alkylidene Chemistry journal August 2009
Rate of interconversion of syn and anti rotamers of Mo(CHCMe2Ph)(NAr)(OR)2 and relative reactivity toward 2,3-bis(trifluoromethyl)norbornadiene journal September 1992
Five-Coordinate Rearrangements of Metallacyclobutane Intermediates during Ring-Opening Metathesis Polymerization of 2,3-Dicarboalkoxynorbornenes by Molybdenum and Tungsten Monoalkoxide Pyrrolide Initiators journal August 2012
The σ-CAM Mechanism: σ Complexes as the Basis of σ-Bond Metathesis at Late-Transition-Metal Centers journal April 2007
Evidence for a direct bonding interaction between titanium and a β-C–H moiety in a titanium–ethyl compound; X-ray crystal structure of [Ti(Me 2 PCH 2 CH 2 PMe 2 )EtCl 3 ] journal January 1982
Understanding Structural and Dynamic Properties of Well-Defined Rhenium-Based Olefin Metathesis Catalysts, Re(⋮CR)(CHR)(X)(Y), from DFT and QM/MM Calculations journal March 2005
DFT calculations of d 0 M(NR)(CHtBu)(X)(Y) (M = Mo, W; R = CPh 3 , 2,6-iPr–C 6 H 3 ; X and Y = CH 2 tBu, OtBu, OSi(OtBu) 3 ) olefin metathesis catalysts: structural, spectroscopic and electronic properties journal January 2006
Two-electron, three-centre carbon–hydrogen–cobalt bonds in the compounds [Co(η-C 5 Me 4 R)(η-C 2 H 4 )(η-C 2 H 4 -µ-H)] BF 4 , R = Me and Et journal January 1983
Intramolecular C–C agostic complexes: C–C sigma interactions by another name journal January 2014
Synthesis and structural characterisation of the first neutral homoleptic lanthanide metal(III) alkyls: [LnR3][Ln = La or Sm, R = CH(SiMe3)2] journal January 1988
Highly reactive organolanthanides. Systematic routes to and olefin chemistry of early and late bis(pentamethylcyclopentadienyl) 4f hydrocarbyl and hydride complexes journal December 1985
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 journal December 1990
Chiral Organolanthanides Designed for Asymmetric Catalysis. Synthesis, Characterization, and Configurational Interconversions of Chiral, C1-Symmetric Organolanthanide Halides, Amides, and Hydrocarbyls journal November 1994
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 journal December 1991
Heteroleptic Tm(II) Complexes:  One More Success for Trofimenko's Scorpionates journal February 2008
Constrained Geometry Organolanthanide Catalysts. Synthesis, Structural Characterization, and Enhanced Aminoalkene Hydroamination/Cyclization Activity journal July 1999
Bis(pentamethylcyclopentadienyl) complexes of cerium(III). Crystal structure of (C5Me5)2CeCH(SiMe3)2 journal December 1988
Organometallic compounds of the lanthanides XCVII. Synthesis and crystal structures of monomeric bis(ethyltetramethylcyclopentadienyl) amide and alkyl derivatives of the lanthanides journal July 1995
Multinuclear magnetic resonance investigation of the fluxionality of CH(SiMe3)2 groups in organolanthanide complexes journal January 1992
Homogeneous and Heterogeneous Catalysis: Bridging the Gap through Surface Organometallic Chemistry journal January 2003
Molecular nature of support effects in single-site heterogeneous catalysts: silica vs. alumina journal January 2011
Silica-supported single-site catalysts: to be or not to be? A conjecture on silica surfaces journal January 2011
State of the Art and Perspectives in the “Molecular Approach” Towards Well-Defined Heterogeneous Catalysts journal March 2014
Surface Organometallic and Coordination Chemistry toward Single-Site Heterogeneous Catalysts: Strategies, Methods, Structures, and Activities journal January 2016
Low co-ordination numbers in lanthanide and actinide compounds. Part I. The preparation and characterization of tris{bis(trimethylsilyl)-amido}lanthanides journal January 1973
Detailed Structural Investigation of the Grafting of [Ta(CH t Bu)(CH 2 t Bu) 3 ] and [Cp*TaMe 4 ] on Silica Partially Dehydroxylated at 700 °C and the Activity of the Grafted Complexes toward Alkane Metathesis journal October 2004
Observation of a H-Agostic Bond in a Highly Active Rhenium–Alkylidene Olefin Metathesis Heterogeneous Catalyst by Two-Dimensional Solid-State NMR Spectroscopy journal December 2002
Direct spectral optimisation of proton–proton homonuclear dipolar decoupling in solid-state NMR journal November 2004
An Improved Broadband Decoupling Sequence for Liquid Crystals and Solids journal January 2000
Ramped-Amplitude Cross Polarization in Magic-Angle-Spinning NMR journal October 1994
ATHENA and ARTEMIS Interactive Graphical Data Analysisusing IFEFFIT journal January 2005
IFEFFIT  : interactive XAFS analysis and FEFF fitting journal March 2001
Multiple-scattering calculations of x-ray-absorption spectra journal July 1995
Generalized gradient approximation for the exchange-correlation hole of a many-electron system journal December 1996
Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation journal September 1992
Erratum: Generalized gradient approximation for the exchange-correlation hole of a many-electron system [Phys. Rev. B 54 , 16 533 (1996)] journal June 1998
Energy‐adjusted a b i n i t i o pseudopotentials for the rare earth elements journal February 1989
The influence of polarization functions on molecular orbital hydrogenation energies journal January 1973
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules journal March 1972
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Théorie quantique des courants interatomiques dans les combinaisons aromatiques journal January 1937
Self-consistent perturbation theory of diamagnetism: I. A gauge-invariant LCAO method for N.M.R. chemical shifts journal April 1974
Self-consistent perturbation theory: Generalization for perturbation-dependent non-orthogonal basis set† This research was partly supported by the Institute of Low Temperatures and Structure Research of the Polish Academy of Sciences. journal December 1977
Natural bond orbital analysis of near‐Hartree–Fock water dimer journal March 1983
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint journal September 1988
An Improved Synthesis of Bis(Trimethylsilyl)Chloromethane journal January 1981
Subvalent Group 4B metal alkyls and amides. Part I. The synthesis and physical properties of kinetically stable bis[bis(trimethysilyl)methyl]-germanium(II), -tin(II), and -lead(II) journal January 1976
Auto-ionization in Lutetium Iodide Complexes:  Effect of the Ionic Radius on Lanthanide−Iodide Binding journal February 2004
Lutetium alkyl and hydride complexes in a non-cyclopentadienyl coordination environment journal January 2007
Reactivity of Trimethylaluminum with Lanthanide Aryloxides:  Adduct and Tetramethylaluminate Formation journal February 2003
Agostic Interactions in d0 Metal Alkyl Complexes journal March 2004
Silicon-carbon agostic interaction with titanium: origin of alkenyl group distortion in Ti[C(SiH2CH3):CH2]X2+. An ab initio MO study journal January 1988
Tertiary phosphine complexes of the f-block metals. Crystal structure of Yb[N(SiMe3)2]2[Me2PCH2CH2PMe2]: evidence for a ytterbium-.gamma.-carbon interaction journal June 1982
A new X-ray crystal structure (100 K) of Yb[N(SiMe 3 ) 2 ] 2 [Me 2 PCH 2 CH 2 PMe 2 ] journal October 2014
C−H Bonds Are Not Elongated by Coordination to Lanthanide Metals:  Single-Crystal Neutron Diffraction Structures of (C 5 Me 5 )Y(OC 6 H 3 t Bu 2 )CH(SiMe 3 ) 2 at 20 K and (C 5 Me 5 )La{CH(SiMe 3 ) 2 } 2 at 15 K journal February 1999
The selective insertion of carbon dioxide into a lanthanide(III) 2,6-di-t-butyl-phenoxide bond journal July 2012
Synthesis, structure and properties of the Cp2Zr{CH(SiMe3)2}+ cation journal November 2006
Sideband intensities in NMR spectra of samples spinning at the magic angle journal December 1980
Novel monopentamethylcyclopentadienyl alkoxides of La and Ce; X-ray crystal structure of (C5Me5Ce(OCMe3)2)2 journal March 1989
On the synthesis of monopentamethylcyclopentadienyl derivatives of yttrium, lanthanum, and cerium journal March 1989
Dynamics of Silica-Supported Catalysts Determined by Combining Solid-State NMR Spectroscopy and DFT Calculations journal May 2008
39. The structure of some electron-deficient molecules journal January 1946
A two-electron hydrogen bridge bond in crystalline trimethylaluminium dimer journal January 1970
Molecular structure and bonding in hexamethyldialuminum journal December 1970
Crystallographic evidence of the three-centre bond in hexamethyldialuminium journal January 1971
On the Nature of the Agostic Bond between Metal Centers and β-Hydrogen Atoms in Alkyl Complexes. An Analysis Based on the Extended Transition State Method and the Natural Orbitals for Chemical Valence Scheme (ETS-NOCV) journal July 2009
γ Agostic C–H or β agostic Si–C bonds in La{CH(SiMe3)2}3? A DFT study of the role of the ligand journal November 2002
High resolution solid state NMRspectroscopy in surface organometallic chemistry: access to molecular understanding of active sites of well-defined heterogeneous catalysts journal January 2008
Nature of Si–H Interactions in a Series of Ruthenium Silazane Complexes Using Multinuclear Solid-State NMR and Neutron Diffraction journal December 2013
Solid-State Synthesis and Characterization of σ-Alkane Complexes, [Rh(L 2 )(η 2 ,η 2 -C 7 H 12 )][BAr F 4 ] (L 2 = Bidentate Chelating Phosphine) journal January 2015
Unravelling the Structure of Magnus’ Pink Salt journal January 2014
Anisotropic NMR Interaction Tensors in the Decamethylaluminocenium Cation journal November 2002
Solid-State 91 Zr NMR Spectroscopy Studies of Zirconocene Olefin Polymerization Catalyst Precursors journal December 2010

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Scandium bis(trimethylsilyl)methyl complexes revisited: extending the 45 Sc NMR chemical shift range and a new structural motif of Li[CH(SiMe 3 ) 2 ] journal January 2020
Rare earth arylsilazido compounds with inequivalent secondary interactions journal January 2018
Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates journal January 2020
Highly selective redistribution of primary arylsilanes to secondary arylsilanes catalyzed by Ln(CH 2 C 6 H 4 NMe 2 - o ) 3 @SBA-15 journal January 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY