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Title: Reactivity of Cyclopentadienyl Molybdenum Compounds towards Formic Acid: Structural Characterization of CpMo(PMe 3 )(CO) 2 H, CpMo(PMe 3 ) 2 (CO)H, [CpMo(μ-O)(μ-O 2 CH)] 2 , and [Cp*Mo(μ-O)(μ-O 2 CH)] 2

Journal Article · · Inorganic Chemistry
 [1]; ORCiD logo [1]
  1. Department of Chemistry, Columbia University, New York, New York 10027, United States
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Here, the molecular structures of CpMo(PMe3)(CO)2H and CpMo(PMe3)2(CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe3)(CO)2H and CpMo(PMe3)2(CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H–Mo–CO moiety are displaced towards the hydride ligand. While CpRMo(PMe3)3–x(CO)xH (CpR = Cp, Cp*; x = 1, 2, 3) are catalysts for the release of H2 from formic acid, the carbonyl derivatives, CpRMo(CO)3H, are also observed to form dinuclear formate compounds, namely, [CpRMo(μ-O)(μ-O2CH)]2. The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O2CH)]2 and [Cp*Mo(μ-O)(μ-O2CH)]2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O2CH)]2 correspond to metal-based δ* (HOMO) and σ (HOMO–1) orbitals. The σ2δ*2 configuration thus corresponds to a formal direct Mo–Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo–Mo bond, whereas a Mo=Mo double bond is required in the absence of lone-pair donation.

Research Organization:
Columbia Univ., New York, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-93ER14339
OSTI ID:
1340022
Alternate ID(s):
OSTI ID: 1344799; OSTI ID: 1425494
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Vol. 56 Journal Issue: 3; ISSN 0020-1669
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

References (130)

Carbonyl abstraction reactions of Cp*Mo(PMe3)3H with CO2, (CH2O)n, HCO2H, and MeOH: the synthesis of Cp*Mo(PMe3)2(CO)H and the catalytic decarboxylation of formic acid journal January 2002
Quantification of “fuzzy” chemical concepts: a computational perspective journal January 2012
Formic acid as a hydrogen source – recent developments and future trends journal January 2012
Charge, bond order and valence in the AB initio SCF theory journal May 1983
Alkyl and aryl derivatives of π-cyclopentadienyl compounds of chromium, molybdenum, tungsten, and iron journal September 1956
Cobalt Phthalocyanine – аn Effective Catalyst of Hydrogen Production from Formic Acid journal January 2009
Piano-stool complexes of the CpML4 type journal January 1982
To Bend or Not to Bend: Electronic Structural Analysis of Linear versus Bent M−H−M Interactions in Dinickel Bis(dialkylphosphino)methane Complexes journal May 2010
Hydrogen generation from formic acid and alcohols using homogeneous catalysts journal January 2010
Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals journal January 1985
Efficient Dehydrogenation of Formic Acid Using an Iron Catalyst journal September 2011
Natural resonance theory: I. General formalism journal April 1998
Theoretical investigation of the metal–metal interaction in dimolybdenum complexes with bridging hydride and methyl ligands journal November 2004
Phosphorus–carbon bond activation of PMe3 at a dimolybdenum center: synthesis and structure of [Cp*Mo(μ-O2CMe)]2(μ-PMe2)(μ-Me) journal January 1998
Mono-η-cyclopentadienylmolybdenum chemistry. Some oxo-, oxohalogeno-, halogeno-, thio-, η-disulphido-, and thiohalogeno-derivatives journal January 1981
Geometric distortions in four-legged piano-stool cyclopentadienyl transition-metal complexes journal January 1993
Synthesis and Reactivity of a Phosphite−Boryl Complex of Molybdenum:  Formation of (η 5 -C 5 Me 5 )Mo(CO) 3 (BH 2 ·phosphite) and Its Mo−B, B−P, and B−H Bond Reactions journal June 2006
Molybdenum(V) complexes with formate: Geometric isomerism of the [Mo2O4Cl2(Py)2(HCOO)]− ion journal November 2013
Natural bond orbital methods: Natural bond orbital methods
  • Glendening, Eric D.; Landis, Clark R.; Weinhold, Frank
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.51
journal June 2011
Nickel-catalyzed release of H 2 from formic acid and a new method for the synthesis of zerovalent Ni(PMe 3 ) 4 journal January 2016
Organometallic conformational equilibriums. XI. cis-trans Isomerism and stereochemical nonrigidity in cyclopentadienylmolybdenum complexes journal October 1970
The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds journal January 2012
Efficient H 2 generation from formic acid using azole complexes in water journal January 2014
Synergic Catalysis of PdCu Alloy Nanoparticles within a Macroreticular Basic Resin for Hydrogen Production from Formic Acid journal July 2015
Unusually Large Tunneling Effect on Highly Efficient Generation of Hydrogen and Hydrogen Isotopes in pH-Selective Decomposition of Formic Acid Catalyzed by a Heterodinuclear Iridium−Ruthenium Complex in Water journal February 2010
Theoretical Study of the Pseudo-Jahn−Teller Effect in the Edge-Sharing Bioctahedral Complex Mo 2 (DXylF) 2 (O 2 CCH 3 ) 2 (μ 2 -O) 2 journal October 2009
Bond Order Analysis Based on the Laplacian of Electron Density in Fuzzy Overlap Space journal March 2013
SHELXT – Integrated space-group and crystal-structure determination journal January 2015
Journey from Mo−Mo Quadruple Bonds to Quintuple Bonds journal August 2009
Bridged and unbridged M2L10 complexes journal July 1980
Study of the exchange phenomenon between two isomers of phosphine substituted carbonyl-π-cyclopentadienyl complexes of molybdenum and tungsten II. Steric influence of bulky groups in phosphines journal September 1970
Hydrogen Storage in Formic Acid – Amine Adducts journal April 2011
A [NiFe]hydrogenase model that catalyses the release of hydrogen from formic acid journal January 2014
Hydrogen storage tanks for vehicles: Recent progress and current status journal April 2011
Distortions in the legs of four-legged piano-stool structures journal June 1990
Experimental and theoretical evidence for double bonds between metal atoms. Dinuclear alkoxo-bridged ditungsten(IV,IV) complexes W2Cl4(OR)4(ROH)2 journal August 1981
X-ray and neutron diffraction studies of tricarbonyl(.eta.-pentamethylcyclopentadienyl)hydridomolybdenum at 163 K journal October 1993
Edge-sharing bioctahedral dimolybdenum(III) molecules with .mu.-RS groups. Direct experimental evidence for spin-state equilibria journal December 1985
Biomass Conversion in Water at 330−410 °C and 30−50 MPa. Identification of Key Compounds for Indicating Different Chemical Reaction Pathways journal January 2003
New approaches to hydrogen storage journal January 2009
A structural study of [CpM(CO)3H] (M = Cr, Mo and W) by single-crystal X-ray diffraction and DFT calculations: sterically crowded yet surprisingly flexible molecules journal January 2009
The current status of hydrogen storage in metal–organic frameworks journal January 2008
Natural resonance theory: II. Natural bond order and valency journal April 1998
Mononuclear octahedral and dinuclear edge-sharing and face-sharing bioctahedral compounds of molybdenum(III). Electronic control on the extent of metal-metal interaction in the dinuclear systems. An equilibrium, structural, and paramagnetic NMR study journal January 1991
Ultrashort metal–metal distances and extreme bond orders journal September 2009
Efficient Catalytic Decomposition of Formic Acid for the Selective Generation of H 2 and H/D Exchange with a Water-Soluble Rhodium Complex in Aqueous Solution journal October 2008
Nature of the M–M bonding (M = Cr, Mo, and W) in [CpM(CO)3]2: Covalent single bond or noncovalent interaction? journal October 2014
The decomposition of formic acid catalysed by soluble metal complexes journal January 1967
Preparation and structural characterization of trirubidium octachlorodimolybdenum. A binuclear structure with strong metal-metal bonding journal May 1969
Breakthroughs in Hydrogen Storage-Formic Acid as a Sustainable Storage Material for Hydrogen journal October 2008
Solution calorimetric, equilibrium, and synthetic studies of oxidative addition/reductive elimination of cyclopentadiene derivatives, C5R5H (R = H, Me, indenyl), to/from the metal complexes M(CO)3(RCN)3/(*5-C5R5)M(CO)3H (M = chromium, molybdenum, tungsten) journal August 1991
Hydrogen Generation at Ambient Conditions: Application in Fuel Cells journal September 2008
Selective Formic Acid Decomposition for High-Pressure Hydrogen Generation: A Mechanistic Study journal February 2009
Interconversion of CO2/H2 and Formic Acid Under Mild Conditions in Water book January 2014
Bond order and valence indices: A personal account journal January 2006
Application of the pople-santry-segal CNDO method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane journal January 1968
On the Usefulness of Bond Orders and Overlap Populations to Chalcogen-Nitrogen Systems journal January 2006
Highly efficient hydrogen evolution by decomposition of formic acid using an iridium catalyst with 4,4′-dihydroxy-2,2′-bipyridine journal January 2009
The Isolation of [Pd{OC(O)H}(H)(NHC)(PR 3 )] (NHC = N-Heterocyclic Carbene) and Its Role in Alkene and Alkyne Reductions Using Formic Acid journal January 2013
A Pseudo-Jahn−Teller Distortion in an Mo 2 (μ 2 -O) 2 Ring Having the Shortest Mo IV −Mo IV Double Bond journal March 2002
Cyclopentadienyl Tricarbonyl Hydrides of Chromium, Molybdenum, and Tungsten [Hydrogen Tricarbonyl(Cyclopentadienyl)Chromate(0), -Molybdate(0), and -Tungstate(0)] book January 2007
The Preparation and Crystal Structure of Dimolybdenum Tetraformate; Photoelectron Spectra of this and Several Other Dimolybdenum Tetracarboxylates journal September 1976
Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi journal January 1985
The heats of hydrogenation of the metal—metal bonded complexes [M(CO)3C5H5]2 (M = Cr, Mo, W) journal March 1985
Carbon dioxide and formic acid—the couple for environmental-friendly hydrogen storage? journal January 2010
Heterogeneous Catalytic Generation of Hydrogen from Formic Acid under Pressurized Aqueous Conditions journal March 2012
A Strong Metal-to-Metal Interaction in an Edge-Sharing Bioctahedral Compound that Leads to a Very Short Tungsten–Tungsten Double Bond journal December 2013
Isolation of Two Agostic Isomers of an Organometallic Cation: Different Structures and Colors journal July 2013
Theoretical analysis of the [Mn 2 (μ-oxo) 2 (μ-carboxylato) 2 ] + core journal January 2004
The Cambridge Structural Database
  • Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179 https://doi.org/10.1107/S2052520616003954
journal April 2016
Hydrogen energy future with formic acid: a renewable chemical hydrogen storage system journal January 2016
Pentabenzylcyclopentadienyl molybdenum and tungsten hydrides: Syntheses, structures and electrochemistry of [MHCpBz(CO)2(L)] (L=CO, PMe3, PPh3) journal May 2010
Unprecedentedly High Formic Acid Dehydrogenation Activity on an Iridium Complex with an N , N ′-Diimine Ligand in Water journal July 2015
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist journal May 2010
Application of the Covalent Bond Classification Method for the Teaching of Inorganic Chemistry journal April 2014
Molecular structures and barriers to internal rotation in bis (.eta.5-cyclopentadienyl)hexacarbonylditungsten and its molybdenum analog journal May 1974
The structures of metal-metal-bonded edge-sharing bioctahedral complexes journal January 1987
Discovering and understanding multiple metal-to-metal bonds journal June 1978
High oxidation state aqueous organometallics: synthesis and structure of a dinuclear oxo(pentamethylcyclopentadienyl)acetato complex of molybdenum(IV), [Cp*Mo(μ-O)(μ-O2CCH3)]2 journal April 2003
Efficient Hydrogen Liberation from Formic Acid Catalyzed by a Well-Defined Iron Pincer Complex under Mild Conditions journal May 2013
Catalytic mechanisms of hydrogen evolution with homogeneous and heterogeneous catalysts journal January 2011
Hydrogen-storage materials for mobile applications journal November 2001
Reactions of the Carbyne-Bridged Radical Complex [Mo 2 (η 5 -C 5 H 5 ) 2 (μ-CPh)(μ-PCy 2 )(μ-CO)] + with Bidentate Ligands Having E–H Bonds (E = O, S, N) journal February 2014
Solid-state isomerisation reactions of (η5-C5H4R)M(CO)2(PR3′)I (M=W, Mo; R=tBu, Me; R′=Ph, OiPr3) journal July 2004
Efficient Disproportionation of Formic Acid to Methanol Using Molecular Ruthenium Catalysts journal August 2014
Exploring the Reactivity of Nickel Pincer Complexes in the Decomposition of Formic Acid to CO 2 /H 2 and the Hydrogenation of NaHCO 3 to HCOONa journal October 2014
Structure of hexacarbonylbis(pentamethylcyclopentadienyl)dimolybdenum(Mo–Mo) journal March 1988
Chemical and Physical Solutions for Hydrogen Storage journal August 2009
An efficient binuclear catalyst for decomposition of formic acid journal January 1998
Electrochemical Studies of Complexes with Oxo- or Hydroxo-Bridged {Mo2(µ-SMe)3}+ Centers: Cleavage of the Oxygen Bridge and Generation of Substrate-Binding Sites journal April 2004
The Lengths of Molybdenum to Molybdenum Quadruple Bonds:  Correlations, Explanations, and Corrections journal May 2002
Potassium, rubidium and ammonium salts of μ-(formato-κ 2 O : O ′)-μ-oxido-bis[oxidobis(peroxido-κ 2 O , O ′)molybdate(VI)] journal December 2012
The MoMo Quintuple Bond as a Ligand to Stabilize Transition-Metal Complexes journal June 2015
The U.S. Department of Energy's National Hydrogen Storage Project: Progress towards meeting hydrogen-powered vehicle requirements journal February 2007
A Well-Defined Iron Catalyst for the Reduction of Bicarbonates and Carbon Dioxide to Formates, Alkyl Formates, and Formamides journal November 2010
The Covalent Bond Classification Method and Its Application to Compounds That Feature 3-Center 2-Electron Bonds book January 2016
A short history of SHELX journal December 2007
CO2-“Neutral” Hydrogen Storage Based on Bicarbonates and Formates journal May 2011
Reversible CO 2 binding triggered by metal–ligand cooperation in a rhenium( i ) PNP pincer-type complex and the reaction with dihydrogen journal January 2014
Charge, bond order and valence in the ab initio SCF theory journal June 1985
Transition metal-organoindium chemistry. Reaction of trialkylindium compounds with (cyclopentadienyl)(tricarbonyl)metal radicals journal March 1991
Liquid-Phase Chemical Hydrogen Storage: Catalytic Hydrogen Generation under Ambient Conditions journal April 2010
Natural bond orbital analysis: A critical overview of relationships to alternative bonding perspectives journal July 2012
A review on biomass-based hydrogen production for renewable energy supply: Biomass-based hydrogen production for renewable energy supply journal August 2015
Trimethylphosphan- und Carbonyl-hydrid-Halbsandwichkomplexe des Chroms, Molybdäns und Wolframs: C5Hf5−, C5Me5− und ein isoelektronischer 6e−-Sauerstof-Tripodligand im Vergleich journal September 1987
Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg journal January 1985
Catalytic interconversion between hydrogen and formic acid at ambient temperature and pressure journal January 2012
Jaguar: A high-performance quantum chemistry software program with strengths in life and materials sciences journal July 2013
Carbon Dioxide-The Hydrogen-Storage Material of the Future? journal October 2008
Iron-Catalyzed Hydrogen Production from Formic Acid journal July 2010
Further considerations on the structure and bonding in edge-sharing bioctahedral complexes journal October 1993
Organometallic oxides: oxidation of [(.eta.-C5Me5)Mo(CO)2]2 with O2 to form syn-[(.eta.-C5Me5)MoCl]2(.mu.-Cl)2(.mu.-O), syn-[(.eta.-C5Me5)MoCl]2(.mu.-Cl)(.mu.-CO3H)(.mu.-O), and [C5Me5O][(.eta.-C5Me5)Mo6O18] journal October 1992
Structure of triammonium μ-formato-(O,O')-di-μ-oxo-bis[diformato(oxo)molybdate(V)] journal December 1987
Aluminium–ligand cooperation promotes selective dehydrogenation of formic acid to H 2 and CO 2 journal January 2014
Reaktivität von Metall-Metall-Bindungen. Bildung und Zerfall einfacher Metallcarbonyl-Zweikernkomplexe als Gleichgewichtsreaktion journal August 1980
(Pentabenzylcyclopentadienyl)molybdenum Complexes: Synthesis, Structures and Redox Properties journal March 2007
A review on exergy comparison of hydrogen production methods from renewable energy sources journal January 2012
Dehydrogenation, disproportionation and transfer hydrogenation reactions of formic acid catalyzed by molybdenum hydride compounds journal January 2015
Hydrogen from renewable electricity: An international review of power-to-gas pilot plants for stationary applications journal February 2013
Hydrogen Storage and Delivery: The Carbon Dioxide – Formic Acid Couple journal September 2011
Metal-metal bonding in pentamethylcyclopentadienylmolybdenum(IV) dinuclear compounds: chloride abstraction from non-bonded Cp∗2Mo2Cl6 to afford bonded [Cp∗2Mo2Cl5]+ journal February 1995
On bond orders and valences in theAb initio quantum chemical theory journal January 1986
A series of edge-sharing bioctahedral, M-M bonded molecules: nonmonotonic bond length variation and its interpretation journal March 1986
Catalytic Disproportionation of Formic Acid to Generate Methanol journal February 2013
Catalytic Generation of Hydrogen from Formic acid and its Derivatives: Useful Hydrogen Storage Materials journal May 2010
Metal-free dehydrogenation of formic acid to H 2 and CO 2 using boron-based catalysts journal January 2015
What Do We Know about the Metal-Metal Bond? journal June 1978
The electronic structure of some polyenes and aromatic molecules. VII. Bonds of fractional order by the molecular orbital method journal February 1939
Subvalent Group 14 metal compounds. Part 10. Syntheses and structures of some bis(metallo)plumbylenes [Pb{Mo(R)(CO) 3 } 2 (OC 4 H 8 )][R =η-C 5 H 5 , η-C 5 H 3 (SiMe 3 ) 2 -1,3, or η-C 5 Me 5 ]; X-ray crystal structures of [Pb{Mo(η-C 5 Me 5 )(CO) 3 } 2 (OC 4 H 8 )] and [{Pb[Mo(η-C 5 Me 5 )(CO) 3 ][Mo(η-C 5 Me 5 )(CO) 2 (µ-CO)]} 2 ] journal January 1987
Photocatalytic Formic Acid Conversion on CdS Nanocrystals with Controllable Selectivity for H 2 or CO journal July 2015

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