Synthesis and Protonation studies of molybdenum(0) bis(dinitrogen) complexes supported by diphosphine ligands containing pendant amines

Liezel A. Labios, Charles J. Weiss, Jonathan D. Egbert, Sheri Lense, R Morris Bullock, William G. Dougherty, W. Scott Kassel, Michael T. Mock

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

A series of molybdenum bis(dinitrogen) complexes of the formula trans-[Mo(N2)2(PEtNRPEt)2] (PEtNRPEt = Et2PCH2N(R)CH2PEt2; R = phenyl (1), 2,6-difluorobenzyl (2), 3,5-difluorobenzyl (3), CH2CH2NMe2 (4), CH2-o-Py (5)] were synthesized and characterized by NMR and IR spectroscopy, and X-ray crystallography. Protonation studies with stoichiometric amounts of triflic acid (HOTf) were performed, and the protonated products were characterized by NMR and in situ IR spectroscopic methods. Products formed in the stepwise protonation reactions included, for example, a mixture of the seven-coordinate molybdenum bis(dinitrogen) hydride, trans-[Mo(H)(N2)2(PEtNPhPEt)2]+ [1H]+, and the Mo-hydrazido triflate complex, trans-[Mo(NNH2)(OTf)(PEtNPhPEt)2]+ [1(NNH2)]+. Complex 2, with more basic pendant amines, can be protonated up to three times, affording the highly-charged molecule, trans-[Mo(H)(N2)2(PEtN2,6-F2-Bn(H)PEt)2)]3+ [2H(PN(H)P)2]3+.

Original languageEnglish
Pages (from-to)105-117
Number of pages13
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume641
Issue number1
DOIs
Publication statusPublished - 2015

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Molybdenum
Protonation
Amines
Ligands
X ray crystallography
Hydrides
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
Nuclear magnetic resonance
Hydrogen
Molecules
trifluoromethanesulfonic acid

Keywords

  • Dinitrogen complex
  • Diphosphine ligands
  • Molybdenum
  • Nitrogen fixation
  • Proton relay

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Synthesis and Protonation studies of molybdenum(0) bis(dinitrogen) complexes supported by diphosphine ligands containing pendant amines. / Labios, Liezel A.; Weiss, Charles J.; Egbert, Jonathan D.; Lense, Sheri; Bullock, R Morris; Dougherty, William G.; Kassel, W. Scott; Mock, Michael T.

In: Zeitschrift fur Anorganische und Allgemeine Chemie, Vol. 641, No. 1, 2015, p. 105-117.

Research output: Contribution to journalArticle

Labios, Liezel A. ; Weiss, Charles J. ; Egbert, Jonathan D. ; Lense, Sheri ; Bullock, R Morris ; Dougherty, William G. ; Kassel, W. Scott ; Mock, Michael T. / Synthesis and Protonation studies of molybdenum(0) bis(dinitrogen) complexes supported by diphosphine ligands containing pendant amines. In: Zeitschrift fur Anorganische und Allgemeine Chemie. 2015 ; Vol. 641, No. 1. pp. 105-117.
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abstract = "A series of molybdenum bis(dinitrogen) complexes of the formula trans-[Mo(N2)2(PEtNRPEt)2] (PEtNRPEt = Et2PCH2N(R)CH2PEt2; R = phenyl (1), 2,6-difluorobenzyl (2), 3,5-difluorobenzyl (3), CH2CH2NMe2 (4), CH2-o-Py (5)] were synthesized and characterized by NMR and IR spectroscopy, and X-ray crystallography. Protonation studies with stoichiometric amounts of triflic acid (HOTf) were performed, and the protonated products were characterized by NMR and in situ IR spectroscopic methods. Products formed in the stepwise protonation reactions included, for example, a mixture of the seven-coordinate molybdenum bis(dinitrogen) hydride, trans-[Mo(H)(N2)2(PEtNPhPEt)2]+ [1H]+, and the Mo-hydrazido triflate complex, trans-[Mo(NNH2)(OTf)(PEtNPhPEt)2]+ [1(NNH2)]+. Complex 2, with more basic pendant amines, can be protonated up to three times, affording the highly-charged molecule, trans-[Mo(H)(N2)2(PEtN2,6-F2-Bn(H)PEt)2)]3+ [2H(PN(H)P)2]3+.",
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AU - Labios, Liezel A.

AU - Weiss, Charles J.

AU - Egbert, Jonathan D.

AU - Lense, Sheri

AU - Bullock, R Morris

AU - Dougherty, William G.

AU - Kassel, W. Scott

AU - Mock, Michael T.

PY - 2015

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N2 - A series of molybdenum bis(dinitrogen) complexes of the formula trans-[Mo(N2)2(PEtNRPEt)2] (PEtNRPEt = Et2PCH2N(R)CH2PEt2; R = phenyl (1), 2,6-difluorobenzyl (2), 3,5-difluorobenzyl (3), CH2CH2NMe2 (4), CH2-o-Py (5)] were synthesized and characterized by NMR and IR spectroscopy, and X-ray crystallography. Protonation studies with stoichiometric amounts of triflic acid (HOTf) were performed, and the protonated products were characterized by NMR and in situ IR spectroscopic methods. Products formed in the stepwise protonation reactions included, for example, a mixture of the seven-coordinate molybdenum bis(dinitrogen) hydride, trans-[Mo(H)(N2)2(PEtNPhPEt)2]+ [1H]+, and the Mo-hydrazido triflate complex, trans-[Mo(NNH2)(OTf)(PEtNPhPEt)2]+ [1(NNH2)]+. Complex 2, with more basic pendant amines, can be protonated up to three times, affording the highly-charged molecule, trans-[Mo(H)(N2)2(PEtN2,6-F2-Bn(H)PEt)2)]3+ [2H(PN(H)P)2]3+.

AB - A series of molybdenum bis(dinitrogen) complexes of the formula trans-[Mo(N2)2(PEtNRPEt)2] (PEtNRPEt = Et2PCH2N(R)CH2PEt2; R = phenyl (1), 2,6-difluorobenzyl (2), 3,5-difluorobenzyl (3), CH2CH2NMe2 (4), CH2-o-Py (5)] were synthesized and characterized by NMR and IR spectroscopy, and X-ray crystallography. Protonation studies with stoichiometric amounts of triflic acid (HOTf) were performed, and the protonated products were characterized by NMR and in situ IR spectroscopic methods. Products formed in the stepwise protonation reactions included, for example, a mixture of the seven-coordinate molybdenum bis(dinitrogen) hydride, trans-[Mo(H)(N2)2(PEtNPhPEt)2]+ [1H]+, and the Mo-hydrazido triflate complex, trans-[Mo(NNH2)(OTf)(PEtNPhPEt)2]+ [1(NNH2)]+. Complex 2, with more basic pendant amines, can be protonated up to three times, affording the highly-charged molecule, trans-[Mo(H)(N2)2(PEtN2,6-F2-Bn(H)PEt)2)]3+ [2H(PN(H)P)2]3+.

KW - Dinitrogen complex

KW - Diphosphine ligands

KW - Molybdenum

KW - Nitrogen fixation

KW - Proton relay

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