Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism

Bezdek, Máté J.; Chirik, Paul J.

doi:10.1021/jacs.8b08460

Title: Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism

Abstract

In this paper, the interconversion of molybdenum ethylene and ethyl complexes by proton-coupled electron transfer (PCET) is described, an unusual transformation in organometallic chemistry. The cationic molybdenum ethylene complex [(^PhTpy)(PPh₂Me)₂Mo(C₂H₄)][BArF²⁴] ([1-C₂H₄]⁺; ^PhTpy = 4'-Ph-2,2',6',2"-terpyridine, ArF²⁴ = [C₆H₃-3,5-(CF₃)₂]₄) was synthesized, structurally characterized, and its electronic structure established by a combination of spectroscopic and computational methods. The overall electronic structure is best described as a molybdenum(III) complex with a metallacyclopropane and a redox neutral terpyridine ligand. Addition of the nonclassical ammine complex [(^PhTpy)(PPh₂Me)₂Mo(NH₃)][BArF²⁴] ([1-NH₃]⁺) to [1-C₂H₄]⁺ resulted in a net C–H bond-forming PCET reaction to yield the molybdenum ethyl [(^PhTpy)(PPh₂Me)₂Mo(CH₂CH₃)][BArF²⁴] ([1-CH₂CH₃]⁺) and amido [(^PhTpy)(PPh₂Me)₂Mo(NH₂)][BArF²⁴] ([1-NH₂]⁺) compounds. The reaction was reversed by addition of 2,4,6-tritert-butylphenoxyl radical to [1-CH₂CH₃]⁺. The solid-state structure of [1-CH₂CH₃]⁺ established a β-agostic ethyl ligand that is maintained in solution as judged by variable temperature ¹H and ¹³C NMR experiments. A combination of variable-temperature NMR experiments and isotopic labeling studies were used to probe the dynamics of [1-CH₂CH₃]⁺ and established restricted β-agostic -CH₃ rotation at low temperature (ΔG^‡ = 9.8 kcal mol^–1 at -86 °C) as well as ethyl isomerization by β-hydride elimination-olefin rotation-reinsertion (ΔH^‡ = 19.3 ± 0.6 kcal mol^–1; ΔS^‡ = 3.4 ± 1.7 cal mol^–1 K^–1). Themore »« less

Authors:

^[1];

^[1]

Princeton Univ., NJ (United States). Department of Chemistry

Publication Date:: 2018-09-27

Research Org.:: Princeton Univ., NJ (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1478323

Grant/Contract Number:: SC0006498

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 140; Journal Issue: 42; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Bezdek, Máté J., and Chirik, Paul J.. Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism.  United States: N. p., 2018. 
Web.  https://doi.org/10.1021/jacs.8b08460.

Copy to clipboard


                    Bezdek, Máté J., & Chirik, Paul J.. Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism.  United States.  https://doi.org/10.1021/jacs.8b08460

Copy to clipboard


                    Bezdek, Máté J., and Chirik, Paul J.. Thu .  
"Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism".  United States.  https://doi.org/10.1021/jacs.8b08460.  https://www.osti.gov/servlets/purl/1478323.

Copy to clipboard


                    
@article{osti_1478323,

  title        = {Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism},

  author       = {Bezdek, Máté J. and Chirik, Paul J.},

  abstractNote = {In this paper, the interconversion of molybdenum ethylene and ethyl complexes by proton-coupled electron transfer (PCET) is described, an unusual transformation in organometallic chemistry. The cationic molybdenum ethylene complex [(PhTpy)(PPh2Me)2Mo(C2H4)][BArF24] ([1-C2H4]+; PhTpy = 4'-Ph-2,2',6',2"-terpyridine, ArF24 = [C6H3-3,5-(CF3)2]4) was synthesized, structurally characterized, and its electronic structure established by a combination of spectroscopic and computational methods. The overall electronic structure is best described as a molybdenum(III) complex with a metallacyclopropane and a redox neutral terpyridine ligand. Addition of the nonclassical ammine complex [(PhTpy)(PPh2Me)2Mo(NH3)][BArF24] ([1-NH3]+) to [1-C2H4]+ resulted in a net C–H bond-forming PCET reaction to yield the molybdenum ethyl [(PhTpy)(PPh2Me)2Mo(CH2CH3)][BArF24] ([1-CH2CH3]+) and amido [(PhTpy)(PPh2Me)2Mo(NH2)][BArF24] ([1-NH2]+) compounds. The reaction was reversed by addition of 2,4,6-tritert-butylphenoxyl radical to [1-CH2CH3]+. The solid-state structure of [1-CH2CH3]+ established a β-agostic ethyl ligand that is maintained in solution as judged by variable temperature 1H and 13C NMR experiments. A combination of variable-temperature NMR experiments and isotopic labeling studies were used to probe the dynamics of [1-CH2CH3]+ and established restricted β-agostic -CH3 rotation at low temperature (ΔG‡ = 9.8 kcal mol–1 at -86 °C) as well as ethyl isomerization by β-hydride elimination-olefin rotation-reinsertion (ΔH‡ = 19.3 ± 0.6 kcal mol–1; ΔS‡ = 3.4 ± 1.7 cal mol–1 K–1). The β-(C–H) bond-dissociation free energy (BDFE) in [1-CH2CH3]+ was determined experimentally as 57 kcal mol–1 (THF) supported by a DFT-computed value of 52 kcal/mol–1 (gas phase). Comparison of pKa and electrochemical data for the complexes [1-C2H4]+ and [1-NH3]+ in combination with a deuterium kinetic isotope effect (kH/kD) of 3.5(2) at 23 °C support a PCET process involving initial electron transfer followed by protonation leading to the formation of [1-CH2CH3]+ and [1-NH2]+ or a concerted pathway. Lastly, the data presented herein provides a structural, thermochemical and mechanistic foundation for understanding the PCET reactivity of organometallic complexes with alkene and alkyl ligands.},

  doi          = {10.1021/jacs.8b08460},

  journal      = {Journal of the American Chemical Society},

  number       = 42,

  volume       = 140,

  place        = {United States},

  year         = {2018},

  month        = {9}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/jacs.8b08460

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 2 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Molecular Catalysts for Water Oxidation
journal, July 2015

Blakemore, James D.; Crabtree, Robert H.; Brudvig, Gary W.
Chemical Reviews, Vol. 115, Issue 23
DOI: 10.1021/acs.chemrev.5b00122

Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds
journal, November 2010

Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y.
Chemical Reviews, Vol. 110, Issue 11
DOI: 10.1021/cr100246c

Cytochrome P450 Compound I: Capture, Characterization, and C-H Bond Activation Kinetics
journal, November 2010

Rittle, J.; Green, M. T.
Science, Vol. 330, Issue 6006
DOI: 10.1126/science.1193478

Reaction of [P ₂ N ₂ ]TaCH ₂ (Me) with Ethylene: Synthesis of [P ₂ N ₂ ]Ta(C ₂ H ₄ )Et, a Neutral Species with a β-Agostic Ethyl Group in Equilibrium with an α-Agostic Ethyl Group ([P ₂ N ₂ ] = PhP(CH ₂ SiMe ₂ NSiMe ₂ CH ₂ ) ₂ PPh)
journal, February 2001

Fryzuk, Michael D.; Johnson, Samuel A.; Rettig, Steven J.
Journal of the American Chemical Society, Vol. 123, Issue 8
DOI: 10.1021/ja0021621

Titanium(IV) Isopropoxide-Catalyzed Formation of 1-Substituted Cyclopropanols in the Reaction of Ethylmagnesium Bromide with Methyl Alkanecarboxylates
journal, January 1991

Kulinkovich, Oleg G.; Sviridov, Sergei V.; Vasilevski, Dmitry A.
Synthesis, Vol. 1991, Issue 03
DOI: 10.1055/s-1991-26431

The crystal and molecular structures of bent bis-π-cyclopentadienyl–metal complexes: (a) bis-π-cyclopentadienyldibromorhenium(V) tetrafluoroborate, (b) bis-π-cyclopentadienyldichloromolybdenum(IV), (c) bis-π-cyclopentadienylhydroxomethylaminomolybdenum(IV) hexafluorophosphate, (d) bis-π-cyclopentadienylethylchloromolybdenum(IV), (e) bis-π-cyclopentadienyldichloroniobium(IV), (f) bis-π-cyclopentadienyldichloromolybdenum(V) tetrafluoroborate, (g) μ-oxo-bis[bis-π-cyclopentadienylchloroniobium(IV)] tetrafluoroborate, (h) bis-π-cyclopentadienyldichlorozirconium
journal, October 1974

Prout, K.; Cameron, T. S.; Forder, R. A.
Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 30, Issue 10
DOI: 10.1107/S0567740874007011

New ansa-2,2-bis(η-cyclopentadienyl)propane molybdenum and tungsten compounds and intramolecular hydrogen–deuterium exchange in methyl-hydride and ethyl-hydride derivatives
journal, January 1997

Chernega, Alexander; Cook, Jessica; Green, Malcolm L. H.
Journal of the Chemical Society, Dalton Transactions, Issue 18
DOI: 10.1039/a703725b

Synthesis of hexanuclear molybdenum cluster alkyl complexes coordinated with trialkylphosphines: crystal structures of trans-[(Mo6Cl8)Cl4{P(n-C4H9)3}2] and all-trans-[(Mo6Cl8)Cl2(C2H5)2{P(n-C4H9)3}2].cntdot.2C6H5CH3
journal, April 1986

Saito, Taro; Nishida, Masakazu; Yamagata, Tsuneaki
Inorganic Chemistry, Vol. 25, Issue 8
DOI: 10.1021/ic00228a011

Molybdenum and Tungsten Structural Differences are Dependent on n d _z _² /( n + 1)s Mixing: Comparisons of (silox) ₃ MX/R (M = Mo, W; silox = ^t Bu ₃ SiO)
journal, July 2008

Kuiper, David S.; Douthwaite, Richard E.; Mayol, Ana-Rita
Inorganic Chemistry, Vol. 47, Issue 16
DOI: 10.1021/ic800139c

Preparation and characterization of 1,2-dialkyl compounds of dimolybdenum and ditungsten of formula M2R2(NMe2)4 (M.tplbond.M)
journal, July 1981

Chisholm, M. H.; Haitko, D. A.; Folting, K.
Journal of the American Chemical Society, Vol. 103, Issue 14
DOI: 10.1021/ja00404a012

Agostic NSiH⋅⋅⋅Mo Complexes: From Curiosity to Catalysis
journal, September 2008

Khalimon, Andrey Y.; Simionescu, Razvan; Kuzmina, Lyudmila G.
Angewandte Chemie International Edition, Vol. 47, Issue 40
DOI: 10.1002/anie.200802147

Organometallic nitrosyl chemistry. 35. Cyclopentadienylethyldinitrosylmolybdate anion, a novel, prototypal 19-electron nitrosyl complex
journal, February 1988

Legzdins, Peter.; Wassink, Berend.; Einstein, Frederick W. B.
Organometallics, Vol. 7, Issue 2
DOI: 10.1021/om00092a038

Nickel-Catalyzed Reductive Cycloisomerization of Enynes with CO ₂
journal, June 2017

Diccianni, Justin B.; Heitmann, Tyler; Diao, Tianning
The Journal of Organic Chemistry, Vol. 82, Issue 13
DOI: 10.1021/acs.joc.7b01034

Decacarbonyl(methyl)hydrotriosmium: NMR evidence for a carbon.cntdot..cntdot.hydrogen.cntdot..cntdot.osmium interaction
journal, November 1978

Calvert, R. Bruce; Shapley, John R.
Journal of the American Chemical Society, Vol. 100, Issue 24
DOI: 10.1021/ja00492a047

Nuclear magnetic resonance studies on partially deuteriated transition metal–methyl derivatives
journal, January 1992

Green, Malcolm L. H.; Hughes, Andrew K.; Popham, Neil A.
J. Chem. Soc., Dalton Trans., Issue 21
DOI: 10.1039/DT9920003077

Formation of η ² C−H Agostic Rhodium Arene Complexes and Their Relevance to Electrophilic Bond Activation
journal, November 1998

Vigalok, Arkadi; Uzan, Olivier; Shimon, Linda J. W.
Journal of the American Chemical Society, Vol. 120, Issue 48
DOI: 10.1021/ja982534u

Reversible Ligand Protonation of a Mn(I) PCP Pincer Complex To Afford a Complex with an η ² -C _aryl –H Agostic Bond
journal, June 2018

Himmelbauer, Daniel; Stöger, Berthold; Veiros, Luis F.
Organometallics, Vol. 37, Issue 20
DOI: 10.1021/acs.organomet.8b00193

Iron PCP Pincer Complexes in Three Oxidation States: Reversible Ligand Protonation To Afford an Fe(0) Complex with an Agostic C–H Arene Bond
journal, June 2018

Himmelbauer, Daniel; Mastalir, Matthias; Stöger, Berthold
Inorganic Chemistry, Vol. 57, Issue 13
DOI: 10.1021/acs.inorgchem.8b01018

Arene C(sp ² )-H Metalation at Ni ^II Modeled with a Reactive PONC _Ph Ligand
journal, July 2016

Jongbloed, Linda S.; García-López, Diego; van Heck, Richard
Inorganic Chemistry, Vol. 55, Issue 16
DOI: 10.1021/acs.inorgchem.6b01162

A Cobalt(I) Pincer Complex with an η ² -C _aryl −H Agostic Bond: Facile C−H Bond Cleavage through Deprotonation, Radical Abstraction, and Oxidative Addition
journal, January 2016

Murugesan, Sathiyamoorthy; Stöger, Berthold; Pittenauer, Ernst
Angewandte Chemie International Edition, Vol. 55, Issue 9
DOI: 10.1002/anie.201510145

Works referencing / citing this record:

A new bis-phenolate mesoionic carbene ligand for early transition metal chemistry
journal, January 2019

Baltrun, Marc; Watt, Fabian A.; Schoch, Roland
Dalton Transactions, Vol. 48, Issue 39
DOI: 10.1039/c9dt03099a

Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer
journal, January 2019

Loose, Florian; Wang, Dian; Tian, Lei
Chemical Communications, Vol. 55, Issue 39
DOI: 10.1039/c9cc01046g

Similar Records in DOE PAGES and OSTI.GOV collections:

Coordination-Induced N–H Bond Weakening in a Molybdenum Pyrrolidine Complex: Isotopic Labeling Provides Insight into the Pathway for H₂ Evolution

Journal Article Bezdek, Máté J. ; Pelczer, István ; Chirik, Paul J. - Organometallics

The synthesis and characterization of a cationic molybdenum pyrrolidine complex is described that exhibits significant coordination-induced N–H bond weakening. Here, the N–H bond dissociation free energy (BDFE) of the coordinated pyrrolidine in [(^PhTpy)(PPh₂Me)₂Mo(NH(pyrr))][BArF²⁴] ([1-NH(pyrr)]⁺; PhTpy = 4'-Ph-2,2',6',2''-terpyridine, NH(pyrr) = pyrrolidine, ArF²⁴ = [C₆H₃-3,5-(CF₃)₂]₄) was determined to be between 41–51 kcal mol^-1 by thermochemical analysis and supported by a density functional theory (DFT) computed value of 48 kcal mol^-1. The complex [1-NH(pyrr)]⁺ underwent proton-coupled electron transfer (PCET) to 2,4,6-tri-tert-butylphenoxyl radical, as well as spontaneous H₂ evolution upon gentle heating to furnish the corresponding molybdenum pyrrolidide complex, [(^PhTpy)(PPh₂Me)₂Mo(N(pyrr))][BArF²⁴] ([1-N(pyrr)]⁺). Thermolysis of themore »« less
https://doi.org/10.1021/acs.organomet.0c00471

Full Text Available
Determination of the N–H Bond Dissociation Free Energy in a Pyridine(diimine)molybdenum Complex Prepared by Proton-Coupled Electron Transfer

Journal Article Margulieux, Grant W. ; Kim, Sangmin ; Chirik, Paul J. - Inorganic Chemistry

The pyridine(diimine) molybdenum bis(imido) complex, (^iPrPDI)Mo(=NTol)₂ (Tol = 4-methylphenyl) was synthesized by addition of two equivalents of 4-methylphenylazide to a corresponding molybdenum benzene derivative, (^iPrPDI)Mo(η⁶-C₆H₆) (^iPrPDI = 2,6-(2,6-iPr₂C₆H₃N=CMe)₂C₅H₃N). Protonation of (^iPrPDI)Mo(=NTol)₂ with 2,6-lutinidum triflate yielded a cationic molybdenum amido complex, [(^iPrPDI)Mo(NHTol)(=NTol)][OTf], which was further transformed into the neutral molybdenum amido complex, (^iPrPDI)Mo(NHTol)(=NTol) by reduction with zinc powder. A series of spectroscopic, synthetic and pK_a determination studies along with electrochemical measurements by the protonation-reduction pathway were used to establish an N–H bond dissociation free energy (BDFE) between 65-69 kcal/mol for the molybdenum imido-amido compound, (^iPrPDI)Mo(NHTol)(=NTol). Full molecule DFT studies provided amore »« less
https://doi.org/10.1021/acs.inorgchem.0c02382

Full Text Available
Reactions of hydrazido(2-) and dinitrogen complexes of molybdenum with reducing agents. Crystal structure of a molybdenum(V) hydrazido(2-) complex: [MoBr[sub 3](NNH[sub 2])(Ph[sub 2]PCH[sub 2]CH[sub 2]PPh[sub 2])][center dot]THF

Journal Article George, T A ; Kaul, B B ; Chen, Qin ; ... - Inorganic Chemistry; (United States)

Tin(II) halides and germanium(II) iodide (known two-electron-reducing agents) have been shown to be effective reducing agents in the transformation of nitrogen hydride intermediates derived from N[sub 2] into ammonia and hydrazine. Addition of SnX[sub 2] (X = Br, Cl), [Et[sub 4]N][SnCl[sub 3]], or GeI[sub 2] to a mixture of trans-[Mo(N[sub 2])[sub 2](PS-diphos)(PPh[sub 2]Me)[sub 2]] (PS-diphos = -P(Ph)CH[sub 2]CH[sub 2]PPh[sub 2] attached to polystyrene-2% divinylbenzene) and HBr in CH[sub 2]Cl[sub 2] (a mixture from which no ammonia is formed) causes substantial amounts of ammonia to be produced. Significant increases in the yield of ammonia were obtained when these same reducing agentsmore »« less
https://doi.org/10.1021/ic00061a028
Calorimetric studies of the heats of protonation of the metal in cis-M(CO)[sub 2](bidentate phosphine)[sub 2] complexes of chromium, molybdenum, and tungsten

Journal Article Sowa, Jr, J R ; Bonanno, J B ; Zanotti, V ; ... - Inorganic Chemistry; (United States)

Titration calorimetry has been used to determine the heats of protonation ([Delta]H[sub HM]) of cis-M(CO)[sub 2](L-L)[sub 2] complexes (M = Cr, Mo, W; L-L = dppm, dppe, dppp, arphos, dmpe) with CF[sub 3]SO[sub 3]H in 1,2 dichloroethane solvent at 25C. Spectroscopic studies show that protonation occurs at the metal center to form [M(H)(CO)[sub 2](L-L)[sub 2]]CF[sub 3]SO[sub 3] complexes with trans CO groups. For the M(CO)[sub 2][Ph[sub 2]P(CH[sub 2])[sub n]PPh[sub 2]][sub 2] complexes, [Delta]H[sub HM] becomes less exothermic as the chelate size increases from n = 1 ([minus]29.7 kcal mol[sup [minus]1]) to n = 3 ([minus]19.0 kcal mol[sup [minus]1]) for Momore »« less
https://doi.org/10.1021/ic00034a015
Synthesis and X-ray crystal structures of (Mo(CO)(Et{sub 2}PC{sub 2}H{sub 4}PEt{sub 2}){sub 2}){sub 2}({mu}-N{sub 2}) with an end-on bridging dinitrogen ligand and Mo(CO)(Bu{sup i}{sub 2}PC{sub 2}H{sub 4}PBu{sup i}{sub 2}){sub 2} containing an agostic Mo...H-C interaction

Journal Article Luo, X L ; Kubas, G J ; Burns, C J ; ... - Inorganic Chemistry

The compound formed by the reaction of trans-Mo(N{sub 2})(Et{sub 2}PC{sub 2}H{sub 4}PEt{sub 2}){sub 2} with ethyl acetate in refluxing toluene under argon has been formulated as the bridging dinitrogen complex (Mo(CO)(Et{sub 2}PC{sub 2}H{sub 4}PEt{sub 2}){sub 2}){sub 2}({mu}-N{sub 2}) (1), in contrast with the previously proposed formulation of Mo(CO)(Et{sub 2}PC{sub 2}H{sub 4}PEt{sub 2}){sub 2} (2). In refluxing p-xylene and under argon, compound 1 eliminates the bridging dinitrogen ligand to form the nitrogen-free compound 2. The reaction of trans-Mo(N{sub 2})(Bu{sup i}{sub 2}PC{sub 2}H{sub 4}PBu{sup i}{sub 2}){sub 2} (3). The molecular structures of compounds 1 and 3 have been determined by single-crystal X-raymore »« less
https://doi.org/10.1021/ic00130a022

Other research related to this record:

Similar Records
Related Works
dataset (4)

Title: Proton-Coupled Electron Transfer to a Molybdenum Ethylene Complex Yields a β-Agostic Ethyl: Structure, Dynamics and Mechanism

Abstract

Citation Formats

Molecular Catalysts for Water Oxidation journal, July 2015

Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds journal, November 2010

Cytochrome P450 Compound I: Capture, Characterization, and C-H Bond Activation Kinetics journal, November 2010

Reaction of [P 2 N 2 ]TaCH 2 (Me) with Ethylene: Synthesis of [P 2 N 2 ]Ta(C 2 H 4 )Et, a Neutral Species with a β-Agostic Ethyl Group in Equilibrium with an α-Agostic Ethyl Group ([P 2 N 2 ] = PhP(CH 2 SiMe 2 NSiMe 2 CH 2 ) 2 PPh) journal, February 2001

Titanium(IV) Isopropoxide-Catalyzed Formation of 1-Substituted Cyclopropanols in the Reaction of Ethylmagnesium Bromide with Methyl Alkanecarboxylates journal, January 1991

New ansa-2,2-bis(η-cyclopentadienyl)propane molybdenum and tungsten compounds and intramolecular hydrogen–deuterium exchange in methyl-hydride and ethyl-hydride derivatives journal, January 1997

Synthesis of hexanuclear molybdenum cluster alkyl complexes coordinated with trialkylphosphines: crystal structures of trans-[(Mo6Cl8)Cl4{P(n-C4H9)3}2] and all-trans-[(Mo6Cl8)Cl2(C2H5)2{P(n-C4H9)3}2].cntdot.2C6H5CH3 journal, April 1986

Molybdenum and Tungsten Structural Differences are Dependent on n d z 2 /( n + 1)s Mixing: Comparisons of (silox) 3 MX/R (M = Mo, W; silox = t Bu 3 SiO) journal, July 2008

Preparation and characterization of 1,2-dialkyl compounds of dimolybdenum and ditungsten of formula M2R2(NMe2)4 (M.tplbond.M) journal, July 1981

Agostic NSiH⋅⋅⋅Mo Complexes: From Curiosity to Catalysis journal, September 2008

Organometallic nitrosyl chemistry. 35. Cyclopentadienylethyldinitrosylmolybdate anion, a novel, prototypal 19-electron nitrosyl complex journal, February 1988

Nickel-Catalyzed Reductive Cycloisomerization of Enynes with CO 2 journal, June 2017

Decacarbonyl(methyl)hydrotriosmium: NMR evidence for a carbon.cntdot..cntdot.hydrogen.cntdot..cntdot.osmium interaction journal, November 1978

Nuclear magnetic resonance studies on partially deuteriated transition metal–methyl derivatives journal, January 1992

Formation of η 2 C−H Agostic Rhodium Arene Complexes and Their Relevance to Electrophilic Bond Activation journal, November 1998

Reversible Ligand Protonation of a Mn(I) PCP Pincer Complex To Afford a Complex with an η 2 -C aryl –H Agostic Bond journal, June 2018

Iron PCP Pincer Complexes in Three Oxidation States: Reversible Ligand Protonation To Afford an Fe(0) Complex with an Agostic C–H Arene Bond journal, June 2018

Arene C(sp 2 )-H Metalation at Ni II Modeled with a Reactive PONC Ph Ligand journal, July 2016

A Cobalt(I) Pincer Complex with an η 2 -C aryl −H Agostic Bond: Facile C−H Bond Cleavage through Deprotonation, Radical Abstraction, and Oxidative Addition journal, January 2016

A new bis-phenolate mesoionic carbene ligand for early transition metal chemistry journal, January 2019

Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer journal, January 2019

Molecular Catalysts for Water Oxidation
journal, July 2015

Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds
journal, November 2010

Cytochrome P450 Compound I: Capture, Characterization, and C-H Bond Activation Kinetics
journal, November 2010

Reaction of [P ₂ N ₂ ]TaCH ₂ (Me) with Ethylene: Synthesis of [P ₂ N ₂ ]Ta(C ₂ H ₄ )Et, a Neutral Species with a β-Agostic Ethyl Group in Equilibrium with an α-Agostic Ethyl Group ([P ₂ N ₂ ] = PhP(CH ₂ SiMe ₂ NSiMe ₂ CH ₂ ) ₂ PPh)
journal, February 2001

Titanium(IV) Isopropoxide-Catalyzed Formation of 1-Substituted Cyclopropanols in the Reaction of Ethylmagnesium Bromide with Methyl Alkanecarboxylates
journal, January 1991

New ansa-2,2-bis(η-cyclopentadienyl)propane molybdenum and tungsten compounds and intramolecular hydrogen–deuterium exchange in methyl-hydride and ethyl-hydride derivatives
journal, January 1997

Synthesis of hexanuclear molybdenum cluster alkyl complexes coordinated with trialkylphosphines: crystal structures of trans-[(Mo6Cl8)Cl4{P(n-C4H9)3}2] and all-trans-[(Mo6Cl8)Cl2(C2H5)2{P(n-C4H9)3}2].cntdot.2C6H5CH3
journal, April 1986

Molybdenum and Tungsten Structural Differences are Dependent on n d _z _² /( n + 1)s Mixing: Comparisons of (silox) ₃ MX/R (M = Mo, W; silox = ^t Bu ₃ SiO)
journal, July 2008

Preparation and characterization of 1,2-dialkyl compounds of dimolybdenum and ditungsten of formula M2R2(NMe2)4 (M.tplbond.M)
journal, July 1981

Agostic NSiH⋅⋅⋅Mo Complexes: From Curiosity to Catalysis
journal, September 2008

Organometallic nitrosyl chemistry. 35. Cyclopentadienylethyldinitrosylmolybdate anion, a novel, prototypal 19-electron nitrosyl complex
journal, February 1988

Nickel-Catalyzed Reductive Cycloisomerization of Enynes with CO ₂
journal, June 2017

Decacarbonyl(methyl)hydrotriosmium: NMR evidence for a carbon.cntdot..cntdot.hydrogen.cntdot..cntdot.osmium interaction
journal, November 1978

Nuclear magnetic resonance studies on partially deuteriated transition metal–methyl derivatives
journal, January 1992

Formation of η ² C−H Agostic Rhodium Arene Complexes and Their Relevance to Electrophilic Bond Activation
journal, November 1998

Reversible Ligand Protonation of a Mn(I) PCP Pincer Complex To Afford a Complex with an η ² -C _aryl –H Agostic Bond
journal, June 2018

Iron PCP Pincer Complexes in Three Oxidation States: Reversible Ligand Protonation To Afford an Fe(0) Complex with an Agostic C–H Arene Bond
journal, June 2018

Arene C(sp ² )-H Metalation at Ni ^II Modeled with a Reactive PONC _Ph Ligand
journal, July 2016

A Cobalt(I) Pincer Complex with an η ² -C _aryl −H Agostic Bond: Facile C−H Bond Cleavage through Deprotonation, Radical Abstraction, and Oxidative Addition
journal, January 2016

A new bis-phenolate mesoionic carbene ligand for early transition metal chemistry
journal, January 2019

Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer
journal, January 2019