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Title: The Synthesis, Characterization and Dehydrogenation of Sigma-Complexes of BN-Cyclohexanes

Journal Article · · Chemistry - A European Journal
 [1];  [2];  [1];  [3];  [3];  [2];  [1]
  1. Univ. of Oxford (United Kingdom). Dept. of Chemistry
  2. Boston College, Chestnut Hill, MA (United States). Dept. of Chemistry
  3. Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
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The coordination chemistry of the 1,2-BN-cyclohexanes 2,2-R2-1,2-B,N-C4H10 (R2=HH, MeH, Me2) with Ir and Rh metal fragments has been studied. This led to the solution (NMR spectroscopy) and solid-state (X-ray diffraction) characterization of [Ir(PCy3)2(H)2(η2η2-H2BNR2C4H8)][BArF4] (NR2=NH2, NMeH) and [Rh(iPr2PCH2CH2CH2PiPr2)(η2η2-H2BNR2C4H8)][BArF4] (NR2=NH2, NMeH, NMe2). For NR2=NH2 subsequent metal-promoted, dehydrocoupling shows the eventual formation of the cyclic tricyclic borazine [BNC4H8]3, via amino-borane and, tentatively characterized using DFT/GIAO chemical shift calculations, cycloborazane intermediates. For NR2=NMeH the final product is the cyclic amino-borane HBNMeC4H8. The mechanism of dehydrogenation of 2,2-H,Me-1,2-B,N-C4H10 using the {Rh(iPr2PCH2CH2CH2PiPr2)}+ catalyst has been probed. Catalytic experiments indicate the rapid formation of a dimeric species, [Rh2(iPr2PCH2CH2CH2PiPr2)2H5][BArF4]. Using the initial rate method starting from this dimer, a first-order relationship to [amine-borane], but half-order to [Rh] is established, which is suggested to be due to a rapid dimer–monomer equilibrium operating.

Research Organization:
Boston College, Chestnut Hill, MA (United States); Univ. of Alabama, Tuscaloosa, AL (United States); Univ. of Oxford (United Kingdom)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Inst. of Environmental Health Sciences (NIEHS) (United States); Rhodes Trust (United Kingdom); Engineering and Physical Sciences Research Council (EPSRC)
Grant/Contract Number:
EE0005658; P30 ES00210; EP/M024210; EP/J02127X
OSTI ID:
1343064
Journal Information:
Chemistry - A European Journal, Vol. 22, Issue 1; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

References (91)

Diborane(4)–metal bonding: between hydrogen bridges and frustrated oxidative addition journal January 2012
B–N compounds for chemical hydrogenstorage journal January 2009
Borane to Boryl Hydride to Borylene Dihydride: Explicit Demonstration of Boron-to-Metal α-Hydride Migration in Aminoborane Activation journal August 2011
NMR: A good tool to ascertain σ-silane or σ-borane formulations? journal November 2008
Structures and Aggregation of the Methylamine−Borane Molecules, Me n H 3− n N·BH 3 ( n = 1−3), Studied by X-ray Diffraction, Gas-Phase Electron Diffraction, and Quantum Chemical Calculations journal February 2009
Generation of aminoborane monomers RR′NBH 2 from amine–boronium cations [RR′NH–BH 2 L] + : metal catalyst-free formation of polyaminoboranes at ambient temperature journal January 2014
Molecular Mechanism for H 2 Release from BH 3 NH 3 , Including the Catalytic Role of the Lewis Acid BH 3 journal February 2007
Cyclic Hydroborate Complexes of Metallocenes III. Syntheses and Structures of Zirconocene Boracyclohexane Derivatives Cp 2 Zr(X){(μ-H) 2 BC 5 H 10 } (X = H, CH 3 , H 2 BC 5 H 10 ) † journal June 1998
Bis(σ-amine-borane) Complexes: An Unusual Binding Mode at a Transition-Metal Center journal September 2009
Ion pairing effects in intramolecular heterolytic H2 activation in an Ir(iii) complex: a combined theoretical/experimental study journal October 2002
[(3,5-(CF3)2C6H3)4B]-[H(OEt2)2]+: a convenient reagent for generation and stabilization of cationic, highly electrophilic organometallic complexes journal November 1992
Monomeric and Oligomeric Amine−Borane σ-Complexes of Rhodium. Intermediates in the Catalytic Dehydrogenation of Amine−Boranes journal October 2009
Rhodium-Catalyzed Boron Arylation of 1,2-Azaborines journal July 2013
Exploring Small Bite-Angle Ligands for the Rhodium-Catalyzed Intermolecular Hydroacylation of β-S-Substituted Aldehydes with 1-Octene and 1-Octyne journal November 2012
Synthese und dynamisches Verhalten von [Rh2(?-H)3H2(PiPr3)4]+. Beitr�ge zur Reaktivit�t des Tetrahydridodirhodium-Komplexes [Rh2H4(PiPr3)4] journal July 1994
Coordination and Dehydrogenation of Amine-Boranes at Metal Centers journal August 2010
Chemistry of Guanidinate-Stabilised Diboranes: Transition-Metal-Catalysed Dehydrocoupling and Hydride Abstraction journal August 2014
The Catalytic Dehydrocoupling of Amine–Boranes and Phosphine–Boranes book January 2015
Dehydrogenation of Diamine-Monoboranes to Cyclic Diaminoboranes: Efficient Ruthenium-Catalyzed Dehydrogenative Cyclization journal February 2012
Molecular Orbital Analysis of the Trend in 11 B NMR Chemical Shifts for (Cp*M) 2 B 5 H 9 (M = Cr, Mo, W; Cp* = η 5 -C 5 Me 5 ) journal February 1999
Development of a Generic Mechanism for the Dehydrocoupling of Amine-Boranes: A Stoichiometric, Catalytic, and Kinetic Study of H 3 B·NMe 2 H Using the [Rh(PCy 3 ) 2 ] + Fragment journal February 2012
Catalysis in service of main group chemistry offers a versatile approach to p-block molecules and materials journal September 2013
Dehydrocoupling of Dimethylamine Borane Catalyzed by Rh(PCy 3 ) 2 H 2 Cl journal March 2013
Koordination und Dehydrierung von Amin-Boran-Addukten an Metallzentren journal August 2010
A combined experimental and computational study of fluxional processes in sigma amine–borane complexes of rhodium and iridium journal January 2014
Development of Rhenium Catalysts for Amine Borane Dehydrocoupling and Transfer Hydrogenation of Olefins journal September 2009
Dehydrogenation Reactions of Cyclic C 2 B 2 N 2 H 12 and C 4 BNH 12 Isomers journal February 2010
Fast Palladium Catalyzed Arylation of Alkenes Using Bulky Monodentate Phosphorus Ligands journal July 1999
Mechanisms of metal-catalyzed dehydrocoupling reactions journal January 2013
A Single-Component Liquid-Phase Hydrogen Storage Material journal December 2011
Mechanism of Metal-Free Hydrogen Transfer between Amine–Boranes and Aminoboranes journal September 2012
Coupling an Electrospray Ionization Mass Spectrometer with a Glovebox: A Straightforward, Powerful, and Convenient Combination for Analysis of Air-Sensitive Organometallics journal July 2008
A comparison of models for calculating nuclear magnetic resonance shielding tensors journal April 1996
Amine–borane dehydrogenation chemistry: Metal-free hydrogen transfer, new catalysts and mechanisms, and the synthesis of polyaminoboranes journal April 2013
Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations journal November 1990
Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation journal February 1992
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Four-Coordinate, 14-Electron Ru II Complexes: Unusual Trigonal Pyramidal Geometry Enforced by Bis(phosphino)silyl Ligation journal August 2011
Safe and Convenient Procedure for Solvent Purification journal January 1996
B-Methyl Amine Borane Derivatives: Synthesis, Characterization, and Hydrogen Release journal January 2014
Mechanism of Intermolecular Ene-yne Metathesis Promoted by the Grubbs First-Generation Catalyst: An Alternative Entry Point to Catalysis journal March 2011
Metal hydrides from cationic rhodium( I ) catalyst precursors. X-Ray structure of [(L–L)HRh(µ-H) 3 RhH(L–L)]ClO 4 [L–L =rac-Fe(η 5 -C 5 H 4 PPhBu t ) 2 ] journal January 1984
Coordinatively unsaturated binuclear clusters of rhodium. The reactivity of [{Pr i 2 P(CH 2 ) n PPr i 2 }Rh] 2 (μ-H) 2 ( n  = 2, 3, and 4) with dihydrogen, and their use in the catalytic hydrogenation of olefins journal May 1989
Transition Metal-Catalyzed Formation of Boron−Nitrogen Bonds:  Catalytic Dehydrocoupling of Amine-Borane Adducts to Form Aminoboranes and Borazines journal August 2003
Ruthenium, Rhodium, and Iridium Bis(σ-B−H) Diisopropylaminoborane Complexes † journal November 2010
1,2-BN Cyclohexane: Synthesis, Structure, Dynamics, and Reactivity journal August 2011
Vinylborane formation in rhodium-catalysed hydroborations; ligand-free homogeneous catalysis journal January 1992
Mechanism of Ruthenium-Catalyzed Hydrogen Transfer Reactions. Concerted Transfer of OH and CH Hydrogens from an Alcohol to a (Cyclopentadienone)ruthenium Complex journal October 2003
Iron Complex-Catalyzed Ammonia–Borane Dehydrogenation. A Potential Route toward B–N-Containing Polymer Motifs Using Earth-Abundant Metal Catalysts journal March 2012
Coordination Compounds of Monoborane−Lewis Base Adducts:  Syntheses and Structures of [M(CO) 5 (η 1 -BH 3 ·L)] (M = Cr, Mo, W; L = NMe 3 , PMe 3 , PPh 3 ) journal December 1999
Amine− and Dimeric Amino−Borane Complexes of the {Rh(P i Pr 3 ) 2 } + Fragment and Their Relevance to the Transition-Metal-Mediated Dehydrocoupling of Amine−Boranes journal February 2010
Tuning the [L2Rh⋯H3B·NR3]+ interaction using phosphine bite angle. Demonstration by the catalytic formation of polyaminoboranes journal January 2011
Synthesis and Structure of a Dichromatetraborane Derivative [{(OC) 4 Cr} 2 (η 4 - H , H ‘, H ‘‘, H ‘‘‘-BH 2 BH 2 ·PMe 2 CH 2 PMe 2 )] journal September 1998
The Role of Chelating Phosphine Rhodium Complexes in Dehydrocoupling Reactions of Amine-Boranes: A Theoretical Investigation Attempting To Rationalize the Observed Behaviors journal March 2014
Ruthenium Bidentate Phosphine Complexes for the Coordination and Catalytic Dehydrogenation of Amine- and Phosphine-Boranes journal June 2011
BH Activation at a Rhodium(I) Center: Isolation of a Bimetallic Complex Relevant to the Transition-Metal-Catalyzed Dehydrocoupling of Amine-Boranes journal November 2009
Recent Advances in Azaborine Chemistry journal May 2012
Rhodium‐Catalyzed Boron Arylation of 1,2‐Azaborines journal July 2013
The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds journal January 2012
Origin of Binding of Ammonia–Borane to Transition-Metal-Based Catalysts: An Insight from the Charge and Energy Decomposition Method ETS-NOCV journal July 2013
Carbon–carbon bond construction using boronic acids and aryl methyl sulfides: orthogonal reactivity in Suzuki-type couplings journal January 2013
Paramagnetic Titanium(III) and Zirconium(III) Metallocene Complexes as Precatalysts for the Dehydrocoupling/Dehydrogenation of Amine-Boranes journal November 2012
A Three-Stage Mechanistic Model for Ammonia–Borane Dehydrogenation by Shvo’s Catalyst journal August 2012
Dehydrogenation of Diamine-Monoboranes to Cyclic Diaminoboranes: Efficient Ruthenium-Catalyzed Dehydrogenative Cyclization journal February 2012
UV-Photoelectron Spectroscopy of 1,2- and 1,3-Azaborines: A Combined Experimental and Computational Electronic Structure Analysis journal June 2012
Amino-borane oligomers bound to a Rh(i) metal fragment journal January 2010
3-Methyl-1,2-BN-cyclopentane: a promising H 2 storage material? journal January 2013
Paramagnetic Titanium(III) and Zirconium(III) Metallocene Complexes as Precatalysts for the Dehydrocoupling/Dehydrogenation of Amine-Boranes journal November 2012
Catching the First Oligomerization Event in the Catalytic Formation of Polyaminoboranes: H 3 B·NMeHBH 2 ·NMeH 2 Bound to Iridium journal July 2011
Revealing the P–B coupling event in the rhodium catalysed dehydrocoupling of phosphine–boranes H3B·PR2H (R = tBu, Ph) journal January 2013
Bis(σ-amine-borane) Complexes: An Unusual Binding Mode at a Transition-Metal Center journal September 2009
Amine− and Phosphine−Borane Adducts: New Interest in Old Molecules journal July 2010
Mechanistic Studies of the Dehydrocoupling and Dehydropolymerization of Amine–Boranes Using a [Rh(Xantphos)] + Catalyst journal June 2014
Fully optimized contracted Gaussian basis sets for atoms Li to Kr journal August 1992
Bis-BN Cyclohexane: A Remarkably Kinetically Stable Chemical Hydrogen Storage Material journal December 2014
Hydrogen Storage by Boron−Nitrogen Heterocycles: A Simple Route for Spent Fuel Regeneration journal March 2010
Dehydrocoupling Reactions of Dimethylamine-Borane by Pt(II) Complexes: A New Mechanism Involving Deprotonation of Boronium Cations
  • Roselló-Merino, Marta; López-Serrano, Joaquín; Conejero, Salvador
  • Journal of the American Chemical Society, Vol. 135, Issue 30 https://doi.org/10.1021/ja404655v
journal July 2013
Jüngste Fortschritte in der Azaborin-Chemie journal May 2012
BH Activation at a Rhodium(I) Center: Isolation of a Bimetallic Complex Relevant to the Transition-Metal-Catalyzed Dehydrocoupling of Amine–Boranes journal January 2010
Characterization of β-B-Agostic Isomers in Zirconocene Amidoborane Complexes journal May 2009
Reaktionen von Buten-(3)-ylaminen mit Boranen journal July 1972
Transition metal complexes of the chelating phosphine borane ligand Ph 2 PCH 2 Ph 2 P·BH 3 journal January 2004
Formation of Trinuclear Rhodium-Hydride Complexes [{Rh(PP*)H} 3 - (μ 2 -H) 3 (μ 3 -H)][anion] 2 -During Asymmetric Hydrogenation? journal April 2013
A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine-Boranes to Cyclic Boranes under Mild Conditions journal July 2015
A tert-butyl-substituted amino-borane bound to an iridium fragment: A latent source of free H2BNtBuH journal December 2012
[Ir(PCy3)2(H)2(H2BNMe2)]+ as a Latent Source of Aminoborane: Probing the Role of Metal in the Dehydrocoupling of H3B⋅NMe2H and Retrodimerisation of [H2BNMe2]2 journal February 2011
The Roles of Dihydrogen Bonds in Amine Borane Chemistry journal July 2013
Computational Study of the Release of H 2 from Ammonia Borane Dimer (BH 3 NH 3 ) 2 and Its Ion Pair Isomers journal September 2007
Computational Study of the Release of H2 from Ammonia Borane Dimer (BH3NH3)2 and Its Ion Pair Isomers. journal November 2007
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density text January 1988
Development of Rhenium Catalysts for Amine Borane Dehydrocoupling and Transfer Hydrogenation of Olefins text January 2009

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
amine-borane
catalysis
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