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 language | English |
|---|---|
| Pages (from-to) | 105-117 |
| Number of pages | 13 |
| Journal | Zeitschrift fur Anorganische und Allgemeine Chemie |
| Volume | 641 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 2015 |
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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 journal › Article
}
TY - JOUR
T1 - Synthesis and Protonation studies of molybdenum(0) bis(dinitrogen) complexes supported by diphosphine ligands containing pendant amines
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
Y1 - 2015
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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U2 - 10.1002/zaac.201400119
DO - 10.1002/zaac.201400119
M3 - Article
VL - 641
SP - 105
EP - 117
JO - Zeitschrift fur Anorganische und Allgemeine Chemie
JF - Zeitschrift fur Anorganische und Allgemeine Chemie
SN - 0044-2313
IS - 1
ER -