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

doi:10.1002/zaac.201400119

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

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article

10 Citations (Scopus)

Abstract

A series of molybdenum bis(dinitrogen) complexes of the formula trans-[Mo(N₂)₂(P^EtN^RP^Et)₂] (P^EtN^RP^Et = 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(P^EtN^PhP^Et)₂]⁺ [1H]⁺, and the Mo-hydrazido triflate complex, trans-[Mo(NNH₂)(OTf)(P^EtN^PhP^Et)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(P^EtN^2,6-F2-Bn(H)P^Et)₂)]³⁺ [2H(PN(H)P)₂]³⁺.

Original language	English
Pages (from-to)	105-117
Number of pages	13
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	641
Issue number	1
DOIs	https://doi.org/10.1002/zaac.201400119
Publication status	Published - Jan 2015

Keywords

Dinitrogen complex
Diphosphine ligands
Molybdenum
Nitrogen fixation
Proton relay

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/zaac.201400119

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Labios, L. A., Weiss, C. J., Egbert, J. D., Lense, S., Bullock, R. M., Dougherty, W. G., Kassel, W. S., & Mock, M. T. (2015). Synthesis and Protonation studies of molybdenum(0) bis(dinitrogen) complexes supported by diphosphine ligands containing pendant amines. Zeitschrift fur Anorganische und Allgemeine Chemie, 641(1), 105-117. https://doi.org/10.1002/zaac.201400119

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, 01.2015, p. 105-117.

Research output: Contribution to journal › Article

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

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+.",

keywords = "Dinitrogen complex, Diphosphine ligands, Molybdenum, Nitrogen fixation, Proton relay",

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

year = "2015",

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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.

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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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