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Title: Mononuclear iridium dinitrogen complexes bonded to zeolite HY

Journal Article · · Chemistry - A European Journal
 [1];  [2];  [1];  [3];  [1]
  1. Univ. of California, Davis, CA (United States). Dept. of Chemical Engineering & Materials Science
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). National Center for Computational Sciences; Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
  3. Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
+ Show Author Affiliations

In this study, the adsorption of N2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridium hydride complexes formed. Here, four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Organization:
DOE Office of Science (SC); USDOE
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1265415
Journal Information:
Chemistry - A European Journal, Vol. 21, Issue 2; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

References (47)

Adsorption of molecular nitrogen on rhodium supported on dealuminated zeolite Y; the formation of well-defined surface dinitrogen complexes journal January 1994
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
A b i n i t i o relativistic effective potentials with spin–orbit operators. IV. Cs through Rn journal November 1990
Infra-red spectra of nitrogen adsorbed on silica-supported platinum
  • Egerton, Terence A.; Sheppard, Norman
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 70, Issue 0 https://doi.org/10.1039/f19747001357
journal January 1974
Dinitrogen Coordination Chemistry:  On the Biomimetic Borderlands journal February 2004
Reactions at Surfaces: From Atoms to Complexity (Nobel Lecture) journal April 2008
Binary Dinitrogen Complexes of Rhodium, Rh(N 2 ) n (where n  = 1–4), in Low Temperature Matrices journal October 1973
Real-Time Characterization of Formation and Breakup of Iridium Clusters in Highly Dealuminated Zeolite Y journal August 2008
A Site-Isolated Iridium Diethylene Complex Supported on Highly Dealuminated Y Zeolite:  Synthesis and Characterization journal September 2007
Energy-consistent pseudopotentials and correlation consistent basis sets for the 5d elements Hf–Pt journal April 2009
Nitrogen Chemisorption on the Coordinatively Unsaturated Rh Site on Al 2 O 3 journal January 1996
Infrared spectroscopy at high pressure. Interaction of nitrogen (N2) with rhodium/aluminum oxide at ambient temperature journal April 1991
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Titanium-Promoted Dinitrogen Cleavage, Partial Hydrogenation, and Silylation journal September 2009
Dinitrogen Cleavage and Hydrogenation by a Trinuclear Titanium Polyhydride Complex journal June 2013
Transformation of Coordinated Dinitrogen by Reaction with Dihydrogen and Primary Silanes journal March 1997
Supported Molecular Iridium Catalysts: Resolving Effects of Metal Nuclearity and Supports as Ligands journal October 2011
"Sideways" Bonded Dinitrogen in Matrix Isolated Cobalt Dinitrogen, CoN 2 journal February 1973
Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex journal May 1995
Binary transition metal dinitrogen complexes. III. Metal-nitrogen stretching modes of Ni(N2)n, Pd(N2)m, and Pt(N2)m (where n = 1-4 and m = 1-3) journal May 1975
Hydrogen Activation and Metal Hydride Formation Trigger Cluster Formation from Supported Iridium Complexes journal March 2012
Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr journal May 1989
Synthesis and crystal structure of Ir(C2H4)2(C5H7O2) journal April 2007
Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion into Imide Species journal November 2007
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Dinitrogen Irreversible Adsorption on Overexchanged Cu-ZSM-5 journal December 2002
A new ONIOM implementation in Gaussian98. Part I. The calculation of energies, gradients, vibrational frequencies and electric field derivatives journal April 1999
Binary Transition Metal Dinitrogen Complexes. Part II. Matrix Infrared and Raman Spectra, Structure, and Bonding of Pt(N 2 ) n (where n  = 1–3) journal August 1973
Efficient Approach for the Computational Study of Alcohol and Nitrile Adsorption in H-ZSM-5 journal February 2012
Reaktionen an Oberflächen: vom Atomaren zum Komplexen (Nobel-Vortrag) journal April 2008
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Binary transition metal dinitrogen complexes. I. Matrix infrared and Raman spectra, structure and bonding of Ni(N2)n and Pd(N2)m(n = 1-4 and m = 1-3) journal January 1973
Binary transition metal nitrogen compounds; infrared evidence for Ni(N2) x journal January 1971
Optimization of parameters for semiempirical methods V: Modification of NDDO approximations and application to 70 elements journal September 2007
Infrared absorption spectra of adsorbed dinitrogen on Ru$z.sbnd;Al2O3$z.sbnd;K below 2000 cm$minus;1 journal August 1981
Strong adsorption of dinitrogen on copper-ion-exchanged mordenite at room temperature journal January 1993
Infra-red spectra of nitrogen adsorbed on iridium journal January 1968
Real-Time Characterization of Formation and Breakup of Iridium Clusters in Highly Dealuminated Zeolite Y journal August 2008
Ab initio relativistic effective potentials with spin‐orbit operators. I. Li through Ar journal March 1985
Chemisorptions of Gases on Iron Synthetic Ammonia Catalysts 1 journal July 1940
Titanium-Promoted Dinitrogen Cleavage, Partial Hydrogenation, and Silylation journal September 2009
Expanding Dinitrogen Reduction Chemistry to Trivalent Lanthanides via the LnZ 3 /Alkali Metal Reduction System:  Evaluation of the Generality of Forming Ln 2 (μ - η 2 : η 2 -N 2 ) Complexes via LnZ 3 /K journal November 2004
Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion into Imide Species journal November 2007
Binary Iron−Dinitrogen Compounds Synthesized by Co-deposition of Mass-Selected Fe, Fe 2 , and Fe 3 with N 2 journal June 2000
Zeolite-Supported Organorhodium Fragments: Essentially Molecular Surface Chemistry Elucidated with Spectroscopy and Theory journal June 2009
Hydrogenation and cleavage of dinitrogen to ammonia with a zirconium complex journal February 2004
N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex journal November 2011

Cited By (2)

High-Energy-Resolution X-ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single-Site Iridium Catalysts journal July 2017
High-Energy-Resolution X-ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single-Site Iridium Catalysts journal August 2017

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
density functional calculations
dinitrogen adsorption
iridium
supported complexes
zeolites