Tungsten and molybdenum dinitrogen complexes supported by a pentadentate tetrapodal phosphine ligand: comparative spectroscopic, electrochemical and reactivity studies

The tungsten dinitrogen complex [W(N 2 )(P Me 2 PP Ph 2 )] ( 2 ) (P Me 2 PP Ph 2 = [2-({bis[3-(diphenylphosphino)propyl]-phosphino}methyl)-2-methylpropane-1,3-diyl]bis(dimethylphosphine)) is synthesized and characterized by X-ray diffraction as well as IR and NMR spectroscopies, showing strong analo...

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Veröffentlicht in:Dalton transactions : an international journal of inorganic chemistry 2022-04, Vol.51 (16), p.6166-6176
Hauptverfasser: Junge, Jannik, Froitzheim, Sven, Engesser, Tobias A, Krahmer, Jan, Näther, Christian, Le Poul, Nicolas, Tuczek, Felix
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container_end_page 6176
container_issue 16
container_start_page 6166
container_title Dalton transactions : an international journal of inorganic chemistry
container_volume 51
creator Junge, Jannik
Froitzheim, Sven
Engesser, Tobias A
Krahmer, Jan
Näther, Christian
Le Poul, Nicolas
Tuczek, Felix
description The tungsten dinitrogen complex [W(N 2 )(P Me 2 PP Ph 2 )] ( 2 ) (P Me 2 PP Ph 2 = [2-({bis[3-(diphenylphosphino)propyl]-phosphino}methyl)-2-methylpropane-1,3-diyl]bis(dimethylphosphine)) is synthesized and characterized by X-ray diffraction as well as IR and NMR spectroscopies, showing strong analogies to its molybdenum analogue [Mo(N 2 )(P Me 2 PP Ph 2 )] ( 1 ). Whereas cyclic voltammetry studies indicate very similar redox potentials, detailed electrochemical and IR-spectroelectrochemical investigations reveal characteristic differences between 1 and 2 upon electrochemical oxidation in THF. Protonation of 2 with HBAr F (BAr F = tetrakis(3,5-bis(trifluoromethyl)-phenyl)borate) leads to the hydrazido(2-) derivative 3 which is spectroscopically characterized as well. In the presence of SmI 2 /H 2 O slightly overstoichiometric conversion of N 2 to ammonia (2.75 equiv.) is observed. Although this is far below the activity of the Mo-complex 1 , it renders 2 the first W complex to produce more than 2 equivalents of NH 3 from N 2 upon addition of protons and reductant. The tungsten dinitrogen complex [W(N 2 )(P Me 2 PP Ph 2 )] is compared to its molybdenum analogue. Detailed (IR-spectro)electrochemical investigations were made. In the presence of SmI 2 /H 2 O the W complex mediates the conversion of N 2 to 2.75 equiv. ammonia.
doi_str_mv 10.1039/d1dt04212b
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Whereas cyclic voltammetry studies indicate very similar redox potentials, detailed electrochemical and IR-spectroelectrochemical investigations reveal characteristic differences between 1 and 2 upon electrochemical oxidation in THF. Protonation of 2 with HBAr F (BAr F = tetrakis(3,5-bis(trifluoromethyl)-phenyl)borate) leads to the hydrazido(2-) derivative 3 which is spectroscopically characterized as well. In the presence of SmI 2 /H 2 O slightly overstoichiometric conversion of N 2 to ammonia (2.75 equiv.) is observed. Although this is far below the activity of the Mo-complex 1 , it renders 2 the first W complex to produce more than 2 equivalents of NH 3 from N 2 upon addition of protons and reductant. The tungsten dinitrogen complex [W(N 2 )(P Me 2 PP Ph 2 )] is compared to its molybdenum analogue. Detailed (IR-spectro)electrochemical investigations were made. 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Whereas cyclic voltammetry studies indicate very similar redox potentials, detailed electrochemical and IR-spectroelectrochemical investigations reveal characteristic differences between 1 and 2 upon electrochemical oxidation in THF. Protonation of 2 with HBAr F (BAr F = tetrakis(3,5-bis(trifluoromethyl)-phenyl)borate) leads to the hydrazido(2-) derivative 3 which is spectroscopically characterized as well. In the presence of SmI 2 /H 2 O slightly overstoichiometric conversion of N 2 to ammonia (2.75 equiv.) is observed. Although this is far below the activity of the Mo-complex 1 , it renders 2 the first W complex to produce more than 2 equivalents of NH 3 from N 2 upon addition of protons and reductant. The tungsten dinitrogen complex [W(N 2 )(P Me 2 PP Ph 2 )] is compared to its molybdenum analogue. Detailed (IR-spectro)electrochemical investigations were made. 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Whereas cyclic voltammetry studies indicate very similar redox potentials, detailed electrochemical and IR-spectroelectrochemical investigations reveal characteristic differences between 1 and 2 upon electrochemical oxidation in THF. Protonation of 2 with HBAr F (BAr F = tetrakis(3,5-bis(trifluoromethyl)-phenyl)borate) leads to the hydrazido(2-) derivative 3 which is spectroscopically characterized as well. In the presence of SmI 2 /H 2 O slightly overstoichiometric conversion of N 2 to ammonia (2.75 equiv.) is observed. Although this is far below the activity of the Mo-complex 1 , it renders 2 the first W complex to produce more than 2 equivalents of NH 3 from N 2 upon addition of protons and reductant. The tungsten dinitrogen complex [W(N 2 )(P Me 2 PP Ph 2 )] is compared to its molybdenum analogue. Detailed (IR-spectro)electrochemical investigations were made. 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source Royal Society Of Chemistry Journals; Alma/SFX Local Collection
subjects Ammonia
Chemical Sciences
Coordination chemistry
Electrochemical oxidation
Molybdenum
Nitrogen compounds
NMR
Nuclear magnetic resonance
Oxidation
Phosphines
Protonation
Reducing agents
Tungsten
title Tungsten and molybdenum dinitrogen complexes supported by a pentadentate tetrapodal phosphine ligand: comparative spectroscopic, electrochemical and reactivity studies
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