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Title: The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes

Abstract

In this study, the coordination chemistry of Mn(CO)5Br was investigated with a series of PNP-pincer ligands. The ligands iPrPONOP (iPrPONOP = 2,6-bis(diisopropylphosphinito)pyridine) and iPrPNHP (iPrPNHP = HN{CH2CH2(PiPr2)}2) gave the desired organometallic manganese complexes (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br, respectively, upon chelation to Mn(CO)5Br. The reactivity of iPrPNNNP (iPrPNNNP = N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine) with Mn(CO)5Br yielded a pair of products, [(iPrPNNNP)Mn(CO)3][Br] and (iPrPNNNCO)Mn(CO)3. The formation of the asymmetric chelate arises from a formal loss of iPr2PBr and C–N bond formation from a carbonyl ligand and NH, yielding a Mn(I) amide core. The nitration reactions of (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br were carried out using silver nitrite, yielding the nitro compounds (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2), respectively. The analogous iron complex (iPrPONOP)Fe(CO)Cl2 was nitrated under the same conditions to yield the salt pair [(iPrPONOP)Fe(CO)2][FeCl3NO]. This reactivity underlines the difference between iso-valent iron and manganese centers. The manganese complexes (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2) were ineffective as oxygen atom transfer reagents for a variety of substrates.

Authors:
 [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1255273
Alternate Identifier(s):
OSTI ID: 1691771
Report Number(s):
LA-UR-16-20260
Journal ID: ISSN 0277-5387
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Polyhedron
Additional Journal Information:
Journal Name: Polyhedron; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Tondreau, Aaron M., and Boncella, James M. The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes. United States: N. p., 2016. Web. doi:10.1016/j.poly.2016.04.007.
Tondreau, Aaron M., & Boncella, James M. The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes. United States. doi:10.1016/j.poly.2016.04.007.
Tondreau, Aaron M., and Boncella, James M. Thu . "The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes". United States. doi:10.1016/j.poly.2016.04.007. https://www.osti.gov/servlets/purl/1255273.
@article{osti_1255273,
title = {The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes},
author = {Tondreau, Aaron M. and Boncella, James M.},
abstractNote = {In this study, the coordination chemistry of Mn(CO)5Br was investigated with a series of PNP-pincer ligands. The ligands iPrPONOP (iPrPONOP = 2,6-bis(diisopropylphosphinito)pyridine) and iPrPNHP (iPrPNHP = HN{CH2CH2(PiPr2)}2) gave the desired organometallic manganese complexes (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br, respectively, upon chelation to Mn(CO)5Br. The reactivity of iPrPNNNP (iPrPNNNP = N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine) with Mn(CO)5Br yielded a pair of products, [(iPrPNNNP)Mn(CO)3][Br] and (iPrPNNNCO)Mn(CO)3. The formation of the asymmetric chelate arises from a formal loss of iPr2PBr and C–N bond formation from a carbonyl ligand and NH, yielding a Mn(I) amide core. The nitration reactions of (iPrPONOP)Mn(CO)2Br and (iPrPNHP)Mn(CO)2Br were carried out using silver nitrite, yielding the nitro compounds (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2), respectively. The analogous iron complex (iPrPONOP)Fe(CO)Cl2 was nitrated under the same conditions to yield the salt pair [(iPrPONOP)Fe(CO)2][FeCl3NO]. This reactivity underlines the difference between iso-valent iron and manganese centers. The manganese complexes (iPrPONOP)Mn(CO)2(NO2) and (iPrPNHP)Mn(CO)2(NO2) were ineffective as oxygen atom transfer reagents for a variety of substrates.},
doi = {10.1016/j.poly.2016.04.007},
journal = {Polyhedron},
number = ,
volume = ,
place = {United States},
year = {2016},
month = {9}
}

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  • Beltrán, Tomás F.; Zaragoza, Guillermo; Delaude, Lionel
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  • Papa, Veronica; Cabrero-Antonino, Jose R.; Alberico, Elisabetta
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Bis(6-Diphenylphosphinoacenaphth-5-yl)Telluride as a Ligand toward Manganese and Rhenium Carbonyls
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journal, December 2017

  • Wei, Duo; Bruneau-Voisine, Antoine; Chauvin, Téo
  • Advanced Synthesis & Catalysis, Vol. 360, Issue 4
  • DOI: 10.1002/adsc.201701115

Hydrogenation of Esters to Alcohols Catalyzed by Defined Manganese Pincer Complexes
journal, September 2016

  • Elangovan, Saravanakumar; Garbe, Marcel; Jiao, Haijun
  • Angewandte Chemie, Vol. 128, Issue 49
  • DOI: 10.1002/ange.201607233

Manganese-Catalyzed Direct Olefination of Methyl-Substituted Heteroarenes with Primary Alcohols
journal, June 2018

  • Barman, Milan K.; Waiba, Satyadeep; Maji, Biplab
  • Angewandte Chemie, Vol. 130, Issue 29
  • DOI: 10.1002/ange.201804729

Highly Active and Selective Manganese C=O Bond Hydrogenation Catalysts: The Importance of the Multidentate Ligand, the Ancillary Ligands, and the Oxidation State
journal, August 2016

  • Kallmeier, Fabian; Irrgang, Torsten; Dietel, Thomas
  • Angewandte Chemie International Edition, Vol. 55, Issue 39
  • DOI: 10.1002/anie.201606218

A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation
journal, April 2017

  • Widegren, Magnus B.; Harkness, Gavin J.; Slawin, Alexandra M. Z.
  • Angewandte Chemie International Edition, Vol. 56, Issue 21
  • DOI: 10.1002/anie.201702406

Manganese(I)-Catalyzed Enantioselective Hydrogenation of Ketones Using a Defined Chiral PNP Pincer Ligand
journal, August 2017

  • Garbe, Marcel; Junge, Kathrin; Walker, Svenja
  • Angewandte Chemie International Edition, Vol. 56, Issue 37
  • DOI: 10.1002/anie.201705471

Reactivity of Silanes with ( t Bu PONOP)Ruthenium Dichloride: Facile Synthesis of Chloro-Silyl Ruthenium Compounds and Formic Acid Decomposition
journal, September 2017

  • Anderson, Nickolas H.; Boncella, James M.; Tondreau, Aaron M.
  • Chemistry - A European Journal, Vol. 23, Issue 55
  • DOI: 10.1002/chem.201703722

{FeNO} 7 -Type Halogenido Nitrosyl Ferrates: Syntheses, Bonding, and Photoinduced Linkage Isomerism
journal, December 2018

  • In-Iam, Areenan; Wolf, Markus; Wilfer, Claudia
  • Chemistry - A European Journal, Vol. 25, Issue 5
  • DOI: 10.1002/chem.201804565

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journal, January 2017

  • Beltrán, Tomás F.; Zaragoza, Guillermo; Delaude, Lionel
  • Dalton Transactions, Vol. 46, Issue 6
  • DOI: 10.1039/c6dt04780g

Efficient and selective hydrogenation of amides to alcohols and amines using a well-defined manganese–PNN pincer complex
journal, January 2017

  • Papa, Veronica; Cabrero-Antonino, Jose R.; Alberico, Elisabetta
  • Chemical Science, Vol. 8, Issue 5
  • DOI: 10.1039/c7sc00138j

Bis(6-Diphenylphosphinoacenaphth-5-yl)Telluride as a Ligand toward Manganese and Rhenium Carbonyls
journal, October 2018


Manganese(I)-Catalyzed Enantioselective Hydrogenation of Ketones Using a Defined Chiral PNP Pincer Ligand
journal, August 2017

  • Garbe, Marcel; Junge, Kathrin; Walker, Svenja
  • Angewandte Chemie, Vol. 129, Issue 37
  • DOI: 10.1002/ange.201705471

A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation
journal, April 2017

  • Widegren, Magnus B.; Harkness, Gavin J.; Slawin, Alexandra M. Z.
  • Angewandte Chemie, Vol. 129, Issue 21
  • DOI: 10.1002/ange.201702406

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Synthesis and characterization of bis- and tris-carbonyl Mn(I) and Re(I) PNP pincer complexes
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  • Glatz, Mathias; Pecak, Jan; Haager, Lena
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  • Kabadwal, Lalit Mohan; Das, Jagadish; Banerjee, Debasis
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