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Title: A Neutrally Charged Trimethylmanganese(III) Complex: Synthesis, Characterization, and Disproportionation Chemistry

Authors:
 [1];  [2];  [3];  [4];  [5];  [1]
  1. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
  2. Department of Biological, Chemical, and Physical Sciences, Roosevelt University, Chicago, Illinois 60605, United States
  3. National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States
  4. Dipartimento di Chimica and INSTM UdR Roma, Università degli Studi di Roma “La Sapienza” P.le A. Moro 5, Roma, I-00185, Italy
  5. Chemical Sciences &, Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1387941
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Organometallics; Journal Volume: 35; Journal Issue: 16; Related Information: CEES partners with Argonne National Laboratory (lead); University of Illinois, Urbana-Champaign; Northwest University
Country of Publication:
United States
Language:
English
Subject:
energy storage (including batteries and capacitors), charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Stalzer, Madelyn M., Telser, Joshua, Krzystek, Jurek, Motta, Alessandro, Delferro, Massimiliano, and Marks, Tobin J. A Neutrally Charged Trimethylmanganese(III) Complex: Synthesis, Characterization, and Disproportionation Chemistry. United States: N. p., 2016. Web. doi:10.1021/acs.organomet.6b00422.
Stalzer, Madelyn M., Telser, Joshua, Krzystek, Jurek, Motta, Alessandro, Delferro, Massimiliano, & Marks, Tobin J. A Neutrally Charged Trimethylmanganese(III) Complex: Synthesis, Characterization, and Disproportionation Chemistry. United States. doi:10.1021/acs.organomet.6b00422.
Stalzer, Madelyn M., Telser, Joshua, Krzystek, Jurek, Motta, Alessandro, Delferro, Massimiliano, and Marks, Tobin J. 2016. "A Neutrally Charged Trimethylmanganese(III) Complex: Synthesis, Characterization, and Disproportionation Chemistry". United States. doi:10.1021/acs.organomet.6b00422.
@article{osti_1387941,
title = {A Neutrally Charged Trimethylmanganese(III) Complex: Synthesis, Characterization, and Disproportionation Chemistry},
author = {Stalzer, Madelyn M. and Telser, Joshua and Krzystek, Jurek and Motta, Alessandro and Delferro, Massimiliano and Marks, Tobin J.},
abstractNote = {},
doi = {10.1021/acs.organomet.6b00422},
journal = {Organometallics},
number = 16,
volume = 35,
place = {United States},
year = 2016,
month = 7
}
  • The synthesis and properties of an unusual, neutrally charged and volatile N,N,N',N'-tetramethylethylenediamine trimethyl manganese(III) complex, (TMEDA)MnMe 3, are described, along with its facile disproportionation to the corresponding Mn(II) and Mn(IV) complexes. Characterization by single-crystal XRD, UV-vis spectroscopy, high-frequency and -field EPR (HFEPR), magnetic susceptibility, and density functional theory (DFT) computations indicate that the (TMEDA)MnMe3 electronic structure can be described as largely square pyramidal Mn(III) centered. The paucity of manganese(III) polyalkyls and the simplicity and reactivity of this compound implicate it as a potentially useful synthetic building block.
  • The synthesis, characterization, and reaction chemistry of a new type of manganese(IV) complex, (PhI(OAc)O)/sub 2/Mn/sup IV/TPP, which hydroxylates alkanes and epoxidizes olefins is reported. This complex contains both a transition metal (Mn) and a nonmetal ion (I) in unusual oxidation states. The high-valent iodine and manganese atoms provide this complex with a five-electron oxidation capability.
  • The cationic complex Cp{sub 2}Zr(CH{sub 3})(THF){sup +} (1, as the BPh{sub 4}{sup {minus}} salt) reacts with 2,6-diethylpyridine to afford the chelated secondary zirconocene-alkyl complex Cp{sub 2}Zr({eta}{sup 2}-C,N-CH(Me)(6-ethylpyrid-2-yl)){sup +} (2). Treatment of complex 2 with CO, CH{sub 3}CN, {sup t}BuCN, and (PhCH{sub 2})(Et){sub 3}N{sup +}Cl{sup {minus}} affords Cp{sub 2}Zr(CH(Me)(6-ethylpyrid-2-yl))(CO){sup +} (3), Cp{sub 2}Zr(CH(Me)(6-ethylpyrid-2-yl))(CH{sub 3}CN){sup +} (4), Cp{sub 2}Zr(CH(Me)(6-ethylpyrid-2-yl))({sup 5}BuCN){sup +} (5), and Cp{sub 2}Zr(CH(Me)(6-ethylpyrid-2-yl))(Cl) (6), respectively. The thermally sensitive d{sup 0} carbonyl complex 3 is a rare example of a d{sup 0} M(alkyl)-CO adduct and is unambiguously characterized in solution by low-temperature NMR and IR spectroscopy, {sup 13}C-labeling and hydrolysis experiments,more » and decomposition studies. IR and NMR data establish that 3 contains a terminal CO ligand. An X-ray structure analysis of 6 established that the CH(Me)(6-ethylpyrid-2-yl) ligand adopts a chelated structure; the similarity of the spectroscopic data for 3-6 implies that 3-5 have similar chelated structures. At room temperature, 3 in CD{sub 2}Cl{sub 2} rapidly decomposes to afford a complex mixture of products. {sup 1}H NMR monitoring of the decomposition of 3 reveals formation of a transient cationic zirconocene-acyl intermediate 9, which undergoes 1,2-H shift to afford a mixture of isomeric/oligomeric zirconocene-enolates. Treatment of this mixture with (PhCH{sub 2})(Et){sub 3}N{sup +}Cl{sup {minus}} affords Cp{sub 2}Zr(OCH=C(Me)(6-ethylpyrid-2-yl)) Cl (10) as a mixture of E/Z isomers, establishing the presence of zirconocene-enolate species. Hydrolysis of the decomposition products of 3 affords a mixture of thermally sensitive tautomers, enol 11/aldehyde 11{prime}, which are characterized by NMR, FTIR, and mass spectroscopy. 39 refs., 6 figs., 3 tabs.« less
  • No abstract prepared.
  • A method is described for the preparation of trimetallic lanthanide polyhydrides via ..beta..-hydrogen elimination from the tert-butyllanthanide complexes in the presence of LiCl. The ir spectrum of the crystalline compound was recorded, and x-ray diffraction studies of the erbium compound identified it as (((C/sub 5/H/sub 5/)/sub 2/ErH)/sub 3/Cl)(Li(THF)/sub 4/). Some discussion of other aspects of the structure of the compounds is included. (BLM)