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Protonation Studies of a Mono-Dinitrogen Complex of Chromium Supported by a 12-Membered Phosphorus Macrocycle Containing Pendant Amines

Journal Article · · Inorganic Chemistry
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  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division, Center for Molecular Electrocatalysis
  2. Villanova Univ. , PA (United States). Dept. of Chemistry
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The reduction of fac-[CrCl3(PPh3NBn3)], (1(Cl3)), (PPh3NBn3 = 1,5,9-tribenzyl-3,7,11-triphenyl-1,5,9-triaza-3,7,11-triphosphacyclododecane) with Mg in the presence of dmpe (dmpe = 1,2-bis(dimethylphosphino)ethane) affords the first example of a monodinitrogen Cr0 complex, Cr(N2)(dmpe)(PPh3NBn3), (2(N2)), containing a pentaphosphine coordination environment. 2(N2) is supported by a unique facially coordinating 12-membered phosphorus macrocycle containing pendant amine groups in the second coordination sphere. Treatment of 2(N2) at –78 °C with 1 equiv of [H(OEt2)2][B(C6F5)4] results in protonation of the metal center, generating the seven-coordinate CrII–N2 hydride complex, [Cr(H)(N2)(dmpe)(PPh3NBn3)][B(C6F5)4], [2(H)(N2)]+. Treatment of 2(15N2) with excess triflic acid at –50 °C afforded a trace amount of 15NH4+ from the reduction of the coordinated 15N2 ligand (electrons originate from Cr). In this work, electronic structure calculations were employed to evaluate the p$$K_a$$ values of three protonated sites of 2(N2) (metal center, pendant amine, and N2 ligand) and were used to predict the thermodynamically preferred Cr-NxHy intermediates in the N2 reduction pathway for 2(N2) and the recently published complex trans-[Cr(N2)2(PPh4NBn4)] upon the addition of protons and electrons.
Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Organization:
Energy Frontier Research Centers (EFRC) (United States)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1386037
Alternate ID(s):
OSTI ID: 1208754
OSTI ID: 1210823
OSTI ID: 1757944
Report Number(s):
PNNL-SA--108000
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 10 Vol. 54; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (68)

Early Transition Metal Complexes of Triphosphorus Macrocycles journal August 2002
Isolation of Pure Diimine journal September 1972
cis-Bis(dinitrogen)tetrakis(trimethylphosphane)chromium journal January 1977
Molybdenum Complexes Supported by Mixed NHC/Phosphine Ligands: Activation of N 2 and Reaction With P(OMe) 3 to the First Meta -Phosphite Complex journal November 2014
Hydride Transfer Reactivity of Mo(L)(H)(depe)2 (L = N, NBEt3) journal February 2006
Octahedral Molybdenum(0) Monodinitrogen Complexes Facially Coordinated by the Tripodal Ligand 1,1,1-Tris(diphenylphosphanylmethyl)ethane - Influence of Diphosphane Coligands on the Activation of N2 journal August 2011
(Dinitrogen)molybdenum Complexes Supported by Asymmetric Silicon-Centered Tripod Ligands: Steric and Electronic Influences on the Coordination of Mono- and Diphosphine Coligands: (Dinitrogen)molybdenum Complexes journal July 2014
6-31G* basis set for third-row atoms journal January 2001
Synthesis and Protonation Studies of Molybdenum(0) Bis(di­nitrogen) Complexes Supported by Diphosphine Ligands ­Containing Pendant Amines: Synthesis and Protonation Studies of Molybdenum(0) Bis(dinitrogen) Complexes journal June 2014
Energy-adjustedab initio pseudopotentials for the second and third row transition elements journal January 1990
Vibrational spectroscopic properties of molybdenum and tungsten N2 and N2Hx complexes with depe coligands: comparison to dppe systems and influence of H-bridges journal October 2003
Fixation of dinitrogen and acetylene by the system CrCl2Mg. isolation and properties of chromium complexes with fixed N2 and C2H2 journal May 1977
Molybdenum(0) dinitrogen complexes with polydentate phosphine ligands for synthetic nitrogen fixation: Geometric and electronic structure contributions to reactivity journal January 2013
Mo– and W–N2 and –CO complexes with novel mixed P/N ligands: Structural properties and implications to synthetic nitrogen fixation journal March 2008
Spectrophotometric Method for Determination of Hydrazine journal December 1952
Phenol-hypochlorite reaction for determination of ammonia journal July 1967
Nitrogenase: A Draft Mechanism journal December 2012
Dinitrogen Coordination Chemistry:  On the Biomimetic Borderlands journal February 2004
Mechanism of Nitrogen Fixation by Nitrogenase: The Next Stage journal January 2014
Recent advances in the chemistry of nitrogen fixation journal December 1978
Reactions of coordinated dinitrogen. 18. Formation of ammonia and hydrazine from the reactions of acids with bis(dinitrogen) complexes of molybdenum. Identification and isolation of intermediates. Possible analogy with the hydrazine-forming property of nitrogenase journal October 1985
Synthesis and properties of cis-bis(dinitrogen)tetrakis(trimethylphosphine)tungsten(0). Crystal and molecular structures of [W(N2)(PMe3)5] and trans-[W(C2H4)2(PMe3)4] journal November 1985
Reactions of coordinated dinitrogen. 21. Synthesis of mono(dinitrogen) complexes of molybdenum. Formation of ammonia and hydrazine journal August 1988
Metal-templated synthesis of macrocyclic (triphosphine)molybdenum complexes journal July 1989
Reactions of mono(dinitrogen) complexes of molybdenum. Isolation and characterization of hydrazido(2-) and mono- and dihydride complexes. Crystal structure of MoBr[PhP(CH2CH2PPh2)2](Me2PCH2PMe2).cntdot.1/2C5H12 journal November 1990
Protonation of Ferrous Dinitrogen Complexes Containing a Diphosphine Ligand with a Pendent Amine journal June 2012
Bonding and Activation of N 2 in Mo(0) Complexes Supported by Hybrid Tripod Ligands with Mixed Dialkylphosphine/Diarylphosphine Donor Groups: Interplay of Steric and Electronic Factors journal May 2013
Oxidation of chromium, molybdenum, and tungsten dicarbonylbis(diphenylphosphino)methane complexes journal October 1975
Seven-coordination. A molecular orbital exploration of structure, stereochemistry, and reaction dynamics journal March 1977
Dinitrogen Activation, Partial Reduction, and Formation of Coordinated Imide Promoted by a Chromium Diiminepyridine Complex journal July 2007
Spectroscopic Characterization of Molybdenum Dinitrogen Complexes Containing a Combination of Di- and Triphosphine Coligands: 31 P NMR Analysis of Five-Spin Systems journal July 2008
Bis(1,2-bis(diphenylphosphino)ethane)tungsten(0) Complexes Containing Electron-Saturated Metal Centers and Singly-Coordinated Bridging Ligands journal January 1996
Reactions of coordinated dinitrogen. 16. New mono-dinitrogen complexes of molybdenum that produce ammonia and hydrazine journal September 1985
Preparation and properties of dinitrogen trimethylphosphine complexes of molybdenum and tungsten. 4. Synthesis, chemical properties, and x-ray structure of cis-[Mo(N2)2(PMe3)4]. The crystal and molecular structures of trans-[Mo(C2H4)2(PMe3)4] and trans,mer-[Mo(C2H4)2(CO)(PMe3)3] journal May 1983
Alkyl, hydride, and dinitrogen 1,2-bis(dimethylphosphino)ethane complexes of chromium. Crystal structures of Me2Cr(dmpe)2, CrH4(dmpe)2, and Cr(N2)2(dmpe)2 journal September 1983
Dynamics of monocapped octahedral [hydro(dicarbonyl)bis(bidentate phosphine)molybdenum])(1+) ions journal July 1978
Dinitrogen Reduction by a Chromium(0) Complex Supported by a 16-Membered Phosphorus Macrocycle journal July 2013
An Acidity Scale for Phosphorus-Containing Compounds Including Metal Hydrides and Dihydrogen Complexes in THF:  Toward the Unification of Acidity Scales journal September 2000
Catalytic Reduction of Dinitrogen to Ammonia by Use of Molybdenum–Nitride Complexes Bearing a Tridentate Triphosphine as Catalysts journal April 2015
Acid−Base Equilibria in Nonpolar Media. 2. 1 Self-Consistent Basicity Scale in THF Solution Ranging from 2-Methoxypyridine to EtP 1 (pyrr) Phosphazene journal March 2002
Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model journal March 1998
Synthesis and Characterization of Hydrido Carbonyl Molybdenum and Tungsten PNP Pincer Complexes journal May 2013
Protonation Studies of a Tungsten Dinitrogen Complex Supported by a Diphosphine Ligand Containing a Pendant Amine journal April 2014
The reduction of mono-coordinated molecular nitrogen to ammonia in a protic environment journal January 1975
Catalytic conversion of nitrogen to ammonia by an iron model complex journal September 2013
A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia journal December 2010
How a century of ammonia synthesis changed the world journal September 2008
Molybdenum dinitrogen complexes supported by a silicon-centred tripod ligand and dppm or dmpm: tuning the activation of N 2 journal January 2014
Preparation and properties of cis-[W(N 2 ) 2 (Ph 2 PCH 2 PPh 2 ) 2 ] and trans-[M(N 2 ) 2 (Ph 2 PCHCHPPh 2 ) 2 ](M = Mo or W), and the crystal structure of cis-[W(N 2 ) 2 (PMe 2 Ph) 4 ] journal January 1985
Dinitrogen, butadiene and related complexes of molybdenum. Crystal structures of [Mo(N 2 )(PMe 3 ) 5 ] and [Mo(η 3 -CH 3 CHCHCH 2 )(η 4 -C 4 H 6 )(PEt 3 ) 2 ][BF 4 ] journal January 1995
The template synthesis of triaryl functionalised 1,5,9-triphosphacyclododecane on molybdenum using organocopper reagents † journal January 1999
A rare terminal dinitrogen complex of chromium journal January 2011
Synthesis and reactivity of molybdenum and tungsten bis(dinitrogen) complexes supported by diphosphine chelates containing pendant amines journal January 2012
The preparation and oxidation, substitution, and protonation reactions of trans-bis(dinitrogen)tetrakis(methyldiphenylphosphine)tungsten journal January 1977
Spectroscopy of terminal dinitrogen complexes: nitrogen-15 and phosphorus-31 nuclear magnetic resonance journal January 1984
Dinitrogen binding and electrochemistry in complexes of molybdenum and tungsten journal January 1984
Synthesis and characterisation of 1,2-bis(dimethylphosphino)ethane (dmpe) complexes of chromium-(0) and -(IV): X-ray crystal structures of trans-Cr(N2)2(dmpe)2, cis-Cr(CO)2(dmpe)2, Cr(C2Ph2)2(dmpe), and CrH4(dmpe)2 journal January 1985
Primary alkenyl phosphine complexes of chromium and molybdenum; synthesis and characterisation of tricarbonyl(1,5,9-triphosphacyclododecane)chromium(0) journal January 1996
Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements journal October 1982
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Unification of reaction pathway and kinetic scheme for N2 reduction catalyzed by nitrogenase journal March 2012
Modified Reagents for Determination of Urea and Ammonia journal April 1962
Density-functional approximation for the correlation energy of the inhomogeneous electron gas journal June 1986
[1,2-Bis(diphenylphosphino)ethane]{2-[bis(diphenylphosphinomethyl)amino]pyridinium}fluoridohydrazidatomolybdenum(IV) bis(tetrafluoridoborate) journal April 2008
Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center journal July 2003
N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex journal November 2011
Bonding, activation, and protonation of dinitrogen on a molybdenum pentaphosphine complex — Comparison to trans -bis(dinitrogen) and -nitrile – dinitrogen complexes with tetraphosphine coordination journal April 2005
Experimental Study of Three-Dimensional Localized Magnetic Reconnection by Use of Merging Torus Plasmas journal January 2009

Cited By (6)

Direct Transformation of Molecular Dinitrogen into Ammonia Catalyzed by Cobalt Dinitrogen Complexes Bearing Anionic PNP Pincer Ligands journal August 2016
Direct Transformation of Molecular Dinitrogen into Ammonia Catalyzed by Cobalt Dinitrogen Complexes Bearing Anionic PNP Pincer Ligands journal August 2016
Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation: Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation journal July 2017
Synthesis and Reactivity of Iron- and Cobalt-Dinitrogen Complexes Bearing PSiP-Type Pincer Ligands toward Nitrogen Fixation journal July 2017
Molybdenum Complexes Supported by PN 3 P Pincer Ligands: Synthesis, Characterization, and Application to Synthetic Nitrogen Fixation : Molybdenum Complexes Supported by PN journal December 2018
Putting chromium on the map for N 2 reduction: production of hydrazine and ammonia. A study of cis-M(N 2 ) 2 (M = Cr, Mo, W) bis(diphosphine) complexes journal January 2016

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chromium
dinitrogen
ammonia
phosphines
pendant amines
bio-inspired
catalysis (heterogeneous)
catalysis (homogeneous)
charge transport
energy storage (including batteries and capacitors)
hydrogen and fuel cells
materials and chemistry by design
solar (fuels)
synthesis (novel materials)