[(MeCN)3Co(C2F5)3]: A Versatile Precursor to Cobalt(III) Perfluoroethyl Complexes

Shreiber, Scott T.; Scudder, John J.; Vicic, David A.

doi:10.1021/acs.organomet.9b00424

Title: [(MeCN)₃Co(C₂F₅)₃]: A Versatile Precursor to Cobalt(III) Perfluoroethyl Complexes

Abstract

The air-stable [fac-(MeCN)3Co(C2F5)3] (1) was prepared through the reaction of cobalt(II) bromide with [Me3Si-C2F5] and AgF. Upon reaction of 1 with wet pyridine, the unexpected product [fac-(H2O)3Co(C2F5)3·6 pyridine] (2) was formed in which water coordinates to cobalt instead of pyridine, and the pyridines form short contacts with each of the hydrogen atoms in the bound water molecules. Facile exchange of the bound acetonitrile ligands in 1 with terpyridine (tpy) and bipyridine (bpy) did occur, however, affording [(tpy)Co(C2F5)3] (5) and [(bpy)Co(C2F5)3(MeCN)] (6) in high yields.

Authors:

^[1]; Scudder, John J. ^[1];

^[1]

Lehigh Univ., Bethlehem, PA (United States)

Publication Date:: 2019-08-08

Research Org.:: Lehigh Univ., Bethlehem, PA (United States)

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

OSTI Identifier:: 1593849

Alternate Identifier(s):: OSTI ID: 1696917

Grant/Contract Number:: SC0009363

Resource Type:: Accepted Manuscript

Journal Name:: Organometallics

Additional Journal Information:: Journal Volume: 38; Journal Issue: 16; Journal ID: ISSN 0276-7333

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; X-rays; Ligands; Pyridines; Solvents; Cobalt

Citation Formats


                    Shreiber, Scott T., Scudder, John J., and Vicic, David A. [(MeCN)3Co(C2F5)3]: A Versatile Precursor to Cobalt(III) Perfluoroethyl Complexes.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.organomet.9b00424.

Copy to clipboard


                    Shreiber, Scott T., Scudder, John J., & Vicic, David A. [(MeCN)3Co(C2F5)3]: A Versatile Precursor to Cobalt(III) Perfluoroethyl Complexes.  United States.  https://doi.org/10.1021/acs.organomet.9b00424

Copy to clipboard


                    Shreiber, Scott T., Scudder, John J., and Vicic, David A. Thu .  
"[(MeCN)3Co(C2F5)3]: A Versatile Precursor to Cobalt(III) Perfluoroethyl Complexes".  United States.  https://doi.org/10.1021/acs.organomet.9b00424.  https://www.osti.gov/servlets/purl/1593849.

Copy to clipboard


                    
@article{osti_1593849,

  title        = {[(MeCN)3Co(C2F5)3]: A Versatile Precursor to Cobalt(III) Perfluoroethyl Complexes},

  author       = {Shreiber, Scott T. and Scudder, John J. and Vicic, David A.},

  abstractNote = {The air-stable [fac-(MeCN)3Co(C2F5)3] (1) was prepared through the reaction of cobalt(II) bromide with [Me3Si-C2F5] and AgF. Upon reaction of 1 with wet pyridine, the unexpected product [fac-(H2O)3Co(C2F5)3·6 pyridine] (2) was formed in which water coordinates to cobalt instead of pyridine, and the pyridines form short contacts with each of the hydrogen atoms in the bound water molecules. Facile exchange of the bound acetonitrile ligands in 1 with terpyridine (tpy) and bipyridine (bpy) did occur, however, affording [(tpy)Co(C2F5)3] (5) and [(bpy)Co(C2F5)3(MeCN)] (6) in high yields.},

  doi          = {10.1021/acs.organomet.9b00424},

  journal      = {Organometallics},

  number       = 16,

  volume       = 38,

  place        = {United States},

  year         = {2019},

  month        = {8}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.organomet.9b00424

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 6 works

Citation information provided by
Web of Science

Figures / Tables:

Figure 1: ORTEP diagram of 1. Selected bond lengths (Å): Co1‐C1 1.971(9); Co1‐C3 1.947(10); Co1‐C5 1.975(9); Co1‐N1 1.974(8); Co1‐N2 2.005(8); Co1‐N3 1.969(8). Selected bond angles (°): C3‐Co1‐N3 94.8(4); C3‐Co1‐C1 90.0(4); N3‐Co1‐C1 175.1(4); C3‐Co1‐N1 87.7(4); N3‐Co1‐N1 86.1(3); C1‐Co1‐N1 94.6(3); C3‐Co1‐C5 91.5(3); N3‐Co1‐C5 88.0(3); C1‐Co1‐C5 91.3(4); N1‐Co1‐C5 174.0(4); C3‐Co1‐N2 173.6(4); N3‐Co1‐N2 86.2(3);more »

All figures and tables (3 total)

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Progress in Difluoroalkylation of Organic Substrates by Visible Light Photoredox Catalysis
journal, January 2019

Lemos, Agostinho; Lemaire, Christian; Luxen, André
Advanced Synthesis & Catalysis, Vol. 361, Issue 7
DOI: 10.1002/adsc.201801121

Transition-Metal (Cu, Pd, Ni)-Catalyzed Difluoroalkylation via Cross-Coupling with Difluoroalkyl Halides
journal, August 2018

Feng, Zhang; Xiao, Yu-Lan; Zhang, Xingang
Accounts of Chemical Research, Vol. 51, Issue 9
DOI: 10.1021/acs.accounts.8b00230

Radical Fluoroalkylation Reactions
journal, June 2018

Barata-Vallejo, Sebastián; Cooke, Maria Victoria; Postigo, Al
ACS Catalysis, Vol. 8, Issue 8
DOI: 10.1021/acscatal.8b02066

The unique fluorine effects in organic reactions: recent facts and insights into fluoroalkylations
journal, January 2016

Ni, Chuanfa; Hu, Jinbo
Chemical Society Reviews, Vol. 45, Issue 20
DOI: 10.1039/C6CS00351F

Organometallic Aspects of Fluoroalkylation Reactions with Copper and Nickel
journal, August 2013

Wang, Huan; Vicic, David
Synlett, Vol. 24, Issue 15
DOI: 10.1055/s-0033-1339435

Perfluoroalkyl Cobaloximes: Preparation Using Hypervalent Iodine Reagents, Molecular Structures, Thermal and Photochemical Reactivity
journal, February 2018

Liebing, Phil; Oehler, Florian; Wagner, Mona
Organometallics, Vol. 37, Issue 4
DOI: 10.1021/acs.organomet.7b00892

Photoinduced Cobalt(III)−Trifluoromethyl Bond Activation Enables Arene C−H Trifluoromethylation
journal, January 2018

Harris, Caleb F.; Kuehner, Christopher S.; Bacsa, John
Angewandte Chemie International Edition, Vol. 57, Issue 5
DOI: 10.1002/anie.201711693

Cobalt Fluorocarbenes: Cycloaddition Reactions with Tetrafluoroethylene and Reactivity of the Perfluorometallacyclic Products
journal, November 2013

Harrison, Daniel J.; Lee, Graham M.; Leclerc, Matthew C.
Journal of the American Chemical Society, Vol. 135, Issue 49
DOI: 10.1021/ja411503c

Cobalt Fluorocarbene Complexes
journal, December 2012

Harrison, Daniel J.; Gorelsky, Serge I.; Lee, Graham M.
Organometallics, Vol. 32, Issue 1
DOI: 10.1021/om3010959

Stepwise addition of difluorocarbene to a transition metal centre
journal, January 2014

Lee, Graham M.; Harrison, Daniel J.; Korobkov, Ilia
Chem. Commun., Vol. 50, Issue 9
DOI: 10.1039/C3CC48468H

Perfluoroalkyl Cobalt(III) Fluoride and Bis(perfluoroalkyl) Complexes: Catalytic Fluorination and Selective Difluorocarbene Formation
journal, December 2015

Leclerc, Matthew C.; Bayne, Julia M.; Lee, Graham M.
Journal of the American Chemical Society, Vol. 137, Issue 51
DOI: 10.1021/jacs.5b12003

Tetracarbonyl(trifluoromethyl)cobalt(I) [Co(CO) ₄ (CF ₃ )] as a Precursor to New Cobalt Trifluoromethyl and Difluorocarbene Complexes
journal, June 2015

Harrison, Daniel J.; Daniels, Alex L.; Korobkov, Ilia
Organometallics, Vol. 34, Issue 18
DOI: 10.1021/acs.organomet.5b00674

Accessing perfluoroalkyl nickel( ii ), ( iii ), and ( iv ) complexes bearing a readily attached [C ₄ F ₈ ] ligand
journal, January 2015

Yu, S.; Dudkina, Y.; Wang, H.
Dalton Transactions, Vol. 44, Issue 45
DOI: 10.1039/C5DT01771H

A Quantitative Scale of the Spectrochemical Series for the Mixed Ligand Complexes of d ⁶ Metals
journal, March 1988

Shimura, Yoichi
Bulletin of the Chemical Society of Japan, Vol. 61, Issue 3
DOI: 10.1246/bcsj.61.693

Universal spectrochemical series of six-coordinate octahedral metal complexes for modifying the ligand field splitting
journal, January 2009

Ishii, Tomohiko; Tsuboi, Shino; Sakane, Genta
Dalton Trans., Issue 4
DOI: 10.1039/B810590A

Highly Trifluoromethylated Platinum Compounds
journal, June 2011

Martínez-Salvador, Sonia; Forniés, Juan; Martín, Antonio
Chemistry - A European Journal, Vol. 17, Issue 29
DOI: 10.1002/chem.201100626

Vicinal fluorine–fluorine coupling constants in perfluoropropyl groups
journal, April 2009

Newmark, Richard A.
Journal of Fluorine Chemistry, Vol. 130, Issue 4
DOI: 10.1016/j.jfluchem.2009.01.005

Fluorine Coupling in Hexafluoroethane
journal, November 1967

Graves, R. E.; Newmark, R. A.
The Journal of Chemical Physics, Vol. 47, Issue 9
DOI: 10.1063/1.1712450

NMR spectra of molecules containing CF2 groups2
journal, August 1968

Harris, R. K.; Woodman, C. M.
Journal of Molecular Spectroscopy, Vol. 26, Issue 4
DOI: 10.1016/S0022-2852(68)80057-8

Figures / Tables found in this record:

Figure 1 (p. 3)

Figure 2 (p. 6)

Figure 3 (p. 8)

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Access to Perfluorometallacyclopentane Complexes of Cobalt through the [(MeCN)₄Co(C₄F₈)][PF₆] Precursor

Journal Article Xue, Teng ; Cramer, Roger E. ; Vicic, David A. - Organometallics

Here, the acetonitrile ligands in [(MeCN)₄Co(C₄F₈)][PF₆] were found to be labile toward ligand substitution reactions, allowing for the preparation of [(MeCN)(tpy)Co(C₄F₈)][PF₆], [(tpy)CoBr(C₄F₈)], [(bpy)₂Co(C₄F₈)][PF₆], and [(cis-κ²-pym-PPh₂)₂Co(C₄F₈)][PF₆] (tpy = 2,2':6',2"-terpyridine, bpy = 2,2'-bipyridine, and pym-PPh₂ = diphenyl(2-pyrimidyl)phosphine). All of the aforementioned complexes have been structurally characterized by X-ray diffraction. Additionally, an improved procedure for the preparation of [(MeCN)₄Co(C₄F₈)][X] (X = PF₆ or BF₄) is reported.
https://doi.org/10.1021/acs.organomet.1c00469

Full Text Available
Electrochemical Reduction of CO ₂ Catalyzed by Re(pyridine-oxazoline)(CO) ₃ Cl Complexes

Journal Article Nganga, John K. ; Samanamu, Christian R. ; Tanski, Joseph M. ; ... - Inorganic Chemistry

In a series of rhenium tricarbonyl complexes coordinated by asymmetric diimine ligands containing a pyridine moiety bound to an oxazoline ring were synthesized, structurally and electrochemically characterized, and screened for CO₂ reduction ability. We reported complexes are of the type Re(N-N)(CO)₃Cl, with N-N = 2-(pyridin-2-yl)-4,5-dihydrooxazole (1), 5-methyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (2), and 5-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole (3). The electrocatalytic reduction of CO₂ by these complexes was observed in a variety of solvents and proceeds more quickly in acetonitrile than in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The analysis of the catalytic cycle for electrochemical CO₂ reduction by 1 in acetonitrile using density functional theory (DFT) supportsmore »« less
Cited by 44
https://doi.org/10.1021/acs.inorgchem.6b02384

Full Text Available
Evidence for dissociative photosubstitution reactions of (Ru(trpy)(bpy)(NCCH sub 3 )) sup 2+. Crystal and molecular structure of (Ru(trpy)(bpy)(py))(PF sub 6 ) sub 2 ter dot (CH sub 3 ) sub 2 CO

Journal Article Hecker, C R ; Fanwick, P E ; McMillin, D R - Inorganic Chemistry; (United States)

In acetonitrile and in the presence of appropriate nucleophiles, the complex (Ru(trpy)(bpy)(NCCH{sub 3})){sup 2+} undergoes a ligand substitution reaction when irradiated into the metal-to-ligand absorption band system (trpy = 2,2{prime}:6{prime},2{double prime}-terpyridine, and bpy = 2,2{prime}-bipyridine.) At 25C quantum yields for displacement of the acetonitrile ligand are 0.0013 (1), 0.0013 (1), and 0.0026 (5) for 1.0 M solutions of pyridine, 4-phenylpyridine, and 2-methylpyridine, respectively. No photochemistry is observed for the osmium(II) analogue, and all findings can be understood in terms of a dissociative reaction mechanism involving a reactive {sup 3}d-d state. The {sup 3}d-d state is accessed from a {sup 3}CTmore »« less
https://doi.org/10.1021/ic00004a013
Ground- and excited-state properties of ruthenium(II) complexes containing tridentate azine ligands, Ru(tpy)(bpy)L{sup 2+}, where L is a polymerizable acetylene

Journal Article Rasmussen, S C ; Ronco, S E ; Mlsna, D A ; ... - Inorganic Chemistry

A series of polypyridyl ruthenium(II) complexes containing monodentate pyridyl- and cyano-substituted acetylenes have been prepared. Complexes of the type Ru(tpy)(bpy)L{sup 2+} (where tpy = 2,2{prime}:6{prime}:2{double_prime}-terpyridine (C{sub 15}H{sub 11}N{sub 3}), bpy = 2,2{prime}-bipyridine (C{sub 10}H{sub 8}N{sub 2}), and L = pyridine (py) (C{sub 5}H{sub 5}N), pyridylacetylene (PA) (C{sub 7}H{sub 5}N), phenylpyridylacetylene (PPA) (C{sub 10}H{sub 9}N), dipyridylacetylene (DPA) (C{sub 12}H{sub 8}N{sub 2}), CH{sub 3}CN, cyanoacetylene (CA) (C{sub 3}HN), and cyanophenylacetylene (CPA) (C{sub 9}H{sub 5}N)) have been prepared, and their synthesis and characterization are reported herein. The complexes [Ru(tpy)(bpy)(PPA)](PF{sub 6}){sub 2}{center_dot}(CH{sub 3}){sub 2}CO, [Ru(tpy)(bpy)(PA)](PF{sub 6}){sub 2}{center_dot}(CH{sub 3}){sub 2}CO, and [Ru(tpy)(bpy)(CH{sub 3}CN)](PF{sub 6}){sub 2}more »« less
https://doi.org/10.1021/ic00108a013
Noninnocent Proton-Responsive Ligand Facilitates Reductive Deprotonation and Hinders CO₂ Reduction Catalysis in [Ru(tpy)(6DHBP)(NCCH₃ )]²⁺ (6DHBP = 6,6'-(OH)₂ bpy)

Journal Article Duan, Lele ; Manbeck, Gerald F. ; Kowalczyk, Marta ; ... - Inorganic Chemistry

Ruthenium complexes with proton-responsive ligands [Ru(tpy)(nDHBP)(NCCH₃)](CF₃SO₃)₂ (tpy = 2,2':6',2"-terpyridine; nDHBP = n,n'-dihydroxy-2,2'-bipyridine, n = 4 or 6) were examined in this study for reductive chemistry and as catalysts for CO₂ reduction. Electrochemical reduction of [Ru(tpy)(nDHBP)(NCCH₃)]²⁺ generates deprotonated species through interligand electron transfer in which the initially formed tpy radical anion reacts with a proton source to produce singly and doubly deprotonated complexes that are identical to those obtained by base titration. A third reduction (i.e., reduction of [Ru(tpy)(nDHBP–2H⁺)]⁰) triggers catalysis of CO₂ reduction; however, the catalytic efficiency is strikingly lower than that of unsubstituted [Ru(tpy)(bpy)(NCCH₃)]²⁺ (bpy = 2,2'-bipyridine). Cyclic voltammetry,more »« less
Cited by 30
https://doi.org/10.1021/acs.inorgchem.6b00398

Full Text Available

Other research related to this record:

CCDC 1936218: Experimental Crystal Structure Determination
dataset, January 2019

T., Shreiber, Scott; J., Scudder, John; A., Vicic, David
Cambridge Crystallographic Data Centre
DOI: 10.5517/ccdc.csd.cc22zsnj
This dataset is a supplement to the current record

CCDC 1936219: Experimental Crystal Structure Determination
dataset, January 2019

T., Shreiber, Scott; J., Scudder, John; A., Vicic, David
Cambridge Crystallographic Data Centre
DOI: 10.5517/ccdc.csd.cc22zspk
This dataset is a supplement to the current record

CCDC 1936220: Experimental Crystal Structure Determination
dataset, January 2019

T., Shreiber, Scott; J., Scudder, John; A., Vicic, David
Cambridge Crystallographic Data Centre
DOI: 10.5517/ccdc.csd.cc22zsql
This dataset is a supplement to the current record

CCDC 1942398: Experimental Crystal Structure Determination
dataset, January 2019

T., Shreiber, Scott; J., Scudder, John; A., Vicic, David
Cambridge Crystallographic Data Centre
DOI: 10.5517/ccdc.csd.cc23670l
This dataset is a supplement to the current record

Similar Records
Related Works
dataset (4)

Title: [(MeCN)3Co(C2F5)3]: A Versatile Precursor to Cobalt(III) Perfluoroethyl Complexes

Abstract

Citation Formats

Figures / Tables:

Progress in Difluoroalkylation of Organic Substrates by Visible Light Photoredox Catalysis journal, January 2019

Transition-Metal (Cu, Pd, Ni)-Catalyzed Difluoroalkylation via Cross-Coupling with Difluoroalkyl Halides journal, August 2018

Radical Fluoroalkylation Reactions journal, June 2018

The unique fluorine effects in organic reactions: recent facts and insights into fluoroalkylations journal, January 2016

Organometallic Aspects of Fluoroalkylation Reactions with Copper and Nickel journal, August 2013

Perfluoroalkyl Cobaloximes: Preparation Using Hypervalent Iodine Reagents, Molecular Structures, Thermal and Photochemical Reactivity journal, February 2018

Photoinduced Cobalt(III)−Trifluoromethyl Bond Activation Enables Arene C−H Trifluoromethylation journal, January 2018

Cobalt Fluorocarbenes: Cycloaddition Reactions with Tetrafluoroethylene and Reactivity of the Perfluorometallacyclic Products journal, November 2013

Cobalt Fluorocarbene Complexes journal, December 2012

Stepwise addition of difluorocarbene to a transition metal centre journal, January 2014

Perfluoroalkyl Cobalt(III) Fluoride and Bis(perfluoroalkyl) Complexes: Catalytic Fluorination and Selective Difluorocarbene Formation journal, December 2015

Tetracarbonyl(trifluoromethyl)cobalt(I) [Co(CO) 4 (CF 3 )] as a Precursor to New Cobalt Trifluoromethyl and Difluorocarbene Complexes journal, June 2015

Accessing perfluoroalkyl nickel( ii ), ( iii ), and ( iv ) complexes bearing a readily attached [C 4 F 8 ] ligand journal, January 2015

A Quantitative Scale of the Spectrochemical Series for the Mixed Ligand Complexes of d 6 Metals journal, March 1988

Universal spectrochemical series of six-coordinate octahedral metal complexes for modifying the ligand field splitting journal, January 2009

Highly Trifluoromethylated Platinum Compounds journal, June 2011

Vicinal fluorine–fluorine coupling constants in perfluoropropyl groups journal, April 2009

Fluorine Coupling in Hexafluoroethane journal, November 1967

NMR spectra of molecules containing CF2 groups2 journal, August 1968

Title: [(MeCN)₃Co(C₂F₅)₃]: A Versatile Precursor to Cobalt(III) Perfluoroethyl Complexes

Progress in Difluoroalkylation of Organic Substrates by Visible Light Photoredox Catalysis
journal, January 2019

Transition-Metal (Cu, Pd, Ni)-Catalyzed Difluoroalkylation via Cross-Coupling with Difluoroalkyl Halides
journal, August 2018

Radical Fluoroalkylation Reactions
journal, June 2018

The unique fluorine effects in organic reactions: recent facts and insights into fluoroalkylations
journal, January 2016

Organometallic Aspects of Fluoroalkylation Reactions with Copper and Nickel
journal, August 2013

Perfluoroalkyl Cobaloximes: Preparation Using Hypervalent Iodine Reagents, Molecular Structures, Thermal and Photochemical Reactivity
journal, February 2018

Photoinduced Cobalt(III)−Trifluoromethyl Bond Activation Enables Arene C−H Trifluoromethylation
journal, January 2018

Cobalt Fluorocarbenes: Cycloaddition Reactions with Tetrafluoroethylene and Reactivity of the Perfluorometallacyclic Products
journal, November 2013

Cobalt Fluorocarbene Complexes
journal, December 2012

Stepwise addition of difluorocarbene to a transition metal centre
journal, January 2014

Perfluoroalkyl Cobalt(III) Fluoride and Bis(perfluoroalkyl) Complexes: Catalytic Fluorination and Selective Difluorocarbene Formation
journal, December 2015

Tetracarbonyl(trifluoromethyl)cobalt(I) [Co(CO) ₄ (CF ₃ )] as a Precursor to New Cobalt Trifluoromethyl and Difluorocarbene Complexes
journal, June 2015

Accessing perfluoroalkyl nickel( ii ), ( iii ), and ( iv ) complexes bearing a readily attached [C ₄ F ₈ ] ligand
journal, January 2015

A Quantitative Scale of the Spectrochemical Series for the Mixed Ligand Complexes of d ⁶ Metals
journal, March 1988

Universal spectrochemical series of six-coordinate octahedral metal complexes for modifying the ligand field splitting
journal, January 2009

Highly Trifluoromethylated Platinum Compounds
journal, June 2011

Vicinal fluorine–fluorine coupling constants in perfluoropropyl groups
journal, April 2009

Fluorine Coupling in Hexafluoroethane
journal, November 1967

NMR spectra of molecules containing CF2 groups2
journal, August 1968