ChemInform Abstract: REACTIVITY OF μ‐(η1:η5‐CYCLOPENTADIENYL)‐TRIS(η‐CYCLOPENTADIENYL)DITITANIUM ((μ‐(η1:η5‐C5H4))(η‐C5H5)3TI2) WITH DINITROGEN. STRUCTURE OF A TITANIUM COMPLEX WITH A TRIPLY COORDINATED DINITROGEN LIGAND

Pez, Guido P.; Apgar, P. A.; Crissey, Richard K.

doi:10.1002/chin.198218283

Cited by 3 publications

(4 citation statements)

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“…1 The conversion of dinitrogen to ammonia has occupied the attention of inorganic chemists for some time. [6][7][8] Ammonia can be detected upon hydrolysis of reduced titanocene complexes, 9 hydrogenation of a dinuclear zirconium derivative, 10 and protonation of certain molybdenum-and iron-dinitrogen complexes. 11,12 The Chatt cycle refers specifically to the protonation of coordinated molybdenum-and tungsten-dinitrogen complexes and represents an enormous amount of work in attempts to model nitrogenase.…”

Section: Introductionmentioning

confidence: 99%

“…The conversion of dinitrogen to ammonia has occupied the attention of inorganic chemists for some time. − Ammonia can be detected upon hydrolysis of reduced titanocene complexes, hydrogenation of a dinuclear zirconium derivative, and protonation of certain molybdenum− and iron−dinitrogen complexes. , The Chatt cycle refers specifically to the protonation of coordinated molybdenum− and tungsten−dinitrogen complexes and represents an enormous amount of work in attempts to model nitrogenase. A few years ago, a catalytic variant was reported that takes advantage of the different solubilities of a reducing agent and an acid to slow down a possible side reaction and allow the protonation of coordinated N 2 to produce ammonia catalytically with four turnovers using a soluble molybdenum catalyst .…”

Section: Introductionmentioning

confidence: 99%

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Side-on End-on Bound Dinitrogen: An Activated Bonding Mode That Facilitates Functionalizing Molecular Nitrogen

2008

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Molecular nitrogen is the source of all of the nitrogen necessary to sustain life on this planet. How it is incorporated into the biosphere is complicated by its intrinsic inertness. For example, biological nitrogen fixation takes N(2) and converts it into ammonia using various nitrogenase enzymes, whereas industrial nitrogen fixation converts N(2) and H(2) to NH(3) using heterogeneous iron or ruthenium surfaces. In both cases, the processes are energy-intensive. Is it possible to discover a homogeneous catalyst that can convert molecular nitrogen into higher-value organonitrogen compounds using a less energy-intensive pathway? If this could be achieved, it would be considered a major breakthrough in this area. In contrast to carbon monoxide, which is reactive and an important feedstock in many homogeneous catalytic reactions, the isoelectronic but inert N(2) molecule is a very poor ligand and not a common industrial feedstock, except for the above-mentioned industrial production of NH(3). Because N(2) is readily available from the atmosphere and because nitrogen is an essential element for the biosphere, attempts to discover new processes involving this simple small molecule have occupied chemists for over a century. Since the first discovery of a dinitrogen complex in 1965, inorganic chemists have been key players in this area and have contributed much fundamental knowledge on structures, binding modes, and reactivity patterns. For the most part, the synthesis of dinitrogen complexes relies on the use of reducing agents to generate an electron-rich intermediate that can interact with this rather inert molecule. In this Account, a facile reaction of dinitrogen with a ditantalum tetrahydride species to generate the unusual side-on end-on bound N(2) moiety is described. This particular process is one of a growing number of new, milder ways to generate dinitrogen complexes. Furthermore, the resulting dinitrogen complex undergoes a number of reactions that expand the known patterns of reactivity for coordinated N(2). This Account reviews the reactions of ([NPN]Ta)(2)(mu-H)(2)(mu-eta(1):eta(2)-N(2)), 2 (where NPN = PhP(CH(2)SiMe(2)NPh)(2)), with a variety of simple hydride reagents, E-H (where E-H = R(2)BH, R(2)AlH, RSiH(3), and Cp(2)ZrCl(H)), each of which results in the cleavage of the N-N bond to form various functionalized imide and nitride moieties. This work is described in the context of a possible catalytic cycle that in principle could generate higher-value nitrogen-containing materials and regenerate the starting ditantalum tetrahydride. How this fails for each particular reagent is discussed and evaluated.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Side-on End-on Bound Dinitrogen: An Activated Bonding Mode That Facilitates Functionalizing Molecular Nitrogen

2008

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“…This coordination mode is rare for a homonuclear species with only three prior reports ( viz . two Ti and one Cu example). − IR spectra of a degassed toluene solution of 3 synthesized using 15 N 2 ( 3- 15 N 2 ) remain unchanged before and after exposure to a 14 N 2 atmosphere even after 3 d (Figure S6). Also, N 2 dissociation and reversion to 2 is not observed as Co 3 N 2 L Et/Me is stable to vacuum and storage under Ar.…”

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confidence: 99%

Dinitrogen Insertion and Cleavage by a Metal–Metal Bonded Tricobalt(I) Cluster

et al. 2021

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Reduction of a tricobalt(II) tri(bromide) cluster supported by a tris(β-diketiminate) cyclophane results in halide loss, ligand compression, and metal–metal bond formation to yield a 48-electron CoI 3 cluster, Co3 L Et/Me (2). Upon reaction of 2 with dinitrogen, all metal–metal bonds are broken, steric conflicts are relaxed, and dinitrogen is incorporated within the internal cavity to yield a formally (μ3-η1:η2:η1-dinitrogen)tricobalt(I) complex, 3. Broken symmetry DFT calculations (PBE0/def2-tzvp/D3) support an N–N bond order of 2.1 in the bound N2 with the calculated N–N stretching frequency (1743 cm–1) comparable to the experimental value (1752 cm–1). Reduction of 3 under Ar in the presence of Me3SiBr results in N2 scission with tris(trimethylsilyl)amine afforded in good yield.

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“…The N–N bond lengths of the two bridging N 2 are 1.175 and 1.178 Å, which are longer than the two terminal N 2 ligands (1.087, 1.051 Å). Compared with dinitrogen-bridged dinuclear complexes, trinuclear complexes with multiple dinitrogen ligands are very rare . When changing the phenyl groups on the phosphorus center in 2a to cyclohexyl groups ( 2b ), dinitrogen-bridged dinuclear complex 3b was generated, probably due to the increase of steric hindrance on the phosphorus center.…”

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Dinitrogen Functionalization Affording Chromium Hydrazido Complex

et al. 2019

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A series of trinuclear and dinuclear Cr(I)− N 2 complexes bearing cyclopentadienyl-phosphine ligands were synthesized and characterized. Further reduction of the Cr(I)−N 2 complexes generated anionic Cr(0)−N 2 complexes, which could react with Me 3 SiCl to afford the first chromium hydrazido complex from N 2 functionalization. These complexes were found to be effective catalysts for the transformation of N 2 into N(SiMe 3 ) 3 .

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ChemInform Abstract: REACTIVITY OF μ‐(η1:η5‐CYCLOPENTADIENYL)‐TRIS(η‐CYCLOPENTADIENYL)DITITANIUM ((μ‐(η1:η5‐C5H4))(η‐C5H5)3TI2) WITH DINITROGEN. STRUCTURE OF A TITANIUM COMPLEX WITH A TRIPLY COORDINATED DINITROGEN LIGAND

Abstract: Der Titelmetallocen‐Komplex (I) zeigt ein stark unterschiedliches Verhalten gegenüber Distickstoff.

Cited by 3 publications

References 1 publication

Side-on End-on Bound Dinitrogen: An Activated Bonding Mode That Facilitates Functionalizing Molecular Nitrogen

Side-on End-on Bound Dinitrogen: An Activated Bonding Mode That Facilitates Functionalizing Molecular Nitrogen

Dinitrogen Insertion and Cleavage by a Metal–Metal Bonded Tricobalt(I) Cluster

Dinitrogen Functionalization Affording Chromium Hydrazido Complex

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