Activation of ammonia and hydrazine by electron rich Fe(ii) complexes supported by a dianionic pentadentate ligand platform through a common terminal Fe(iii) amido intermediate

Synopsis: a highly reactive Fe(iii)–NH2 complex is generated via activation of ammonia or hydrazine in reactions of relevance to fundamental steps in ammonia oxidation processes mediated by an abundant, first row transition metal.

Transition metal complexes with thiosemicarbazide-based ligands, Part II, Synthesis and characterisation of nickel(II), cobalt(II), manganese(II) and zinc(II) complexes with the pentadentate ligand, 2,6-diacetylpyridine bis(S-methylisothiosemicarbazone)

Transition Metal Chemistry ◽

10.1007/bf01023835 ◽

1987 ◽

Vol 12 (6) ◽

pp. 504-507 ◽

Cited By ~ 5

Author(s):

Vukadin M. Leovac ◽

Valerija I. Cešljević

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Tandem Deoxygenative Hydrosilation of Carbon Dioxide with a Cationic Scandium Hydridoborate and B(C6F5)3

10.26434/chemrxiv.10267739.v1 ◽

2019 ◽

Author(s):

Daniel W. Beh ◽

Warren Piers ◽

Benjamin S. Gelfand ◽

Jian-Bin Lin

Keyword(s):

Carbon Dioxide ◽

Transition Metal ◽

Room Temperature ◽

Starting Material ◽

Metal Component ◽

Hydride Complex ◽

Hydride Abstraction ◽

Pentadentate Ligand ◽

Hb C

A scandium hydridoborate complex supported by the dianionic pentadentate ligand B2Pz4Py is prepared via hydride abstraction from the previously reported scandium hydride complex with tris-pentafluorophenyl borane. Exposure of [(B2Pz4Py)Sc][HB(C6F5)3] to CO2 immediately forms [(B2Pz4Py)Sc][HCOOB(C6F5)3] at room temperature. The formatoborate complex can also be synthesized directly from the starting material (B2Pz4Py)ScCl with Et3SiH and B(C6F5)3 while in the presence of an atmosphere of CO2 in 81% yield. This compound was evaluated as the transition metal component of a tandem deoxgenative CO2 hydrosilation catalyst. At 5% loadings, complete consumption of Et3SiH was observed along with CO2 reduction products, but conversion to an inactive scandium complex identified as (B2Pz4Py)ScOSiEt3 was observed

First-Row Transition-Metal Complexes of a New Pentadentate Ligand, α,α,α′,α′-Tetra(pyrazolyl)lutidine

Inorganic Chemistry ◽

10.1021/ic801093q ◽

2008 ◽

Vol 47 (17) ◽

pp. 7468-7470 ◽

Cited By ~ 15

Author(s):

Tyler J. Morin ◽

Brian Bennett ◽

Sergey V. Lindeman ◽

James R. Gardinier

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Transition-Metal Complexes with Sulfur Ligands. 132.1Electron-Rich Fe and Ru Complexes with [MN2S3] Cores Containing the New Pentadentate Ligand ‘N2H2S3‘2-(= 2,2‘-Bis(2-mercaptophenylamino)diethyl Sulfide(2−))

Inorganic Chemistry ◽

10.1021/ic980383q ◽

1999 ◽

Vol 38 (3) ◽

pp. 459-466 ◽

Cited By ~ 22

Author(s):

Dieter Sellmann ◽

Jürgen Utz ◽

Frank W. Heinemann

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Diethyl Sulfide ◽

Ru Complexes ◽

Recent advances in waste water treatment through transition metal sulfides-based advanced oxidation processes

Water Research ◽

10.1016/j.watres.2021.116850 ◽

2021 ◽

Vol 192 ◽

pp. 116850

Author(s):

Yangju Li ◽

Haoran Dong ◽

Long Li ◽

Lin Tang ◽

Ran Tian ◽

...

Keyword(s):

Waste Water ◽

Water Treatment ◽

Transition Metal ◽

Advanced Oxidation Processes ◽

Waste Water Treatment ◽

Advanced Oxidation ◽

Metal Sulfides ◽

Transition Metal Sulfides ◽

Oxidation Processes ◽

Recent Advances

Übergangsmetallkomplexe mit Schwefelliganden, XI* Molybdän-Oxo-Komplexe des Typs [Mo(IV)(O)(S2)2], [Mo(VI)(O)2(S4)], [MO(IV)(O)(S4)] und [Mo(IV)(O)(S5)] mit zwei-, vier- und fünfzähnigen Thioether-thiolat-Liganden (Sx = mehrzähniger Thioether-thiolat-Ligand) / Transition Metal Complexes with Sulfur Ligands, XI* Molybdenum Oxo Complexes of the Type [Mo(IV)(O)(S2)2], [Mo(VI)(O)2(S4)], [MO(IV)(O)(S4)] and [Mo(IV)(O) (S5)] with Bi-, Tetra- and Pentadentate Thioether-Thiolate Ligands (SX = Multidentate Thioether-Thiolate Ligand

Zeitschrift für Naturforschung B ◽

10.1515/znb-1985-0310 ◽

1985 ◽

Vol 40 (3) ◽

pp. 368-372 ◽

Cited By ~ 6

Author(s):

Dieter Sellmann ◽

Lothar Zapf

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Analogous Reaction ◽

Thiolate Ligands ◽

Oxo Complexes ◽

Reductive Nitrosylation ◽

Thiolate Ligand ◽

Thiol Ligand ◽

MoClReacting [Mo(O)2(acac)2] (acac- = acetylacetonate) with the tetradentate thioether-thiol ligand 2,3,8.9-dibenzo-1,4,7,10-tetrathiadecane (dttd-H2) yields cis-[Mo(O)2(dttd)] ; this compound is reduced by PPh3 to give [MoO(dttd)], which is also obtained from [MoCl2(dttd)] and H2O. Depending upon the concentrations of the reactants [4(THF)2], CH3SC6H4SH and H2O , in THF the products [MoO(CH3SC6H4S)2] or [MoCl2(CH3SC6H4S)2] are formed. In the analogous reaction between [MoCl4(THF)2] and the pentadentate ligand 2,3,11,12-dibenzo- 1,4,7,10,13-pentathiatridecane (dpttd-H2) in THF/H2O. [MoO(dpttd)] is obtained exclusively. Due to their poor solubility, the Mo(IV)-oxo complexes show only limited reactivity only; with NO reductive nitrosylation to cis-Mo(NO)2 complexes is observed.

Activation of Ammonia and Hydrazine by Electron Rich Fe(II) Complexes Supported by a Dianionic Pentadentate Ligand Platform Through a Common Terminal Fe(III) Amido Intermediate

10.26434/chemrxiv.13249889.v1 ◽

2020 ◽

Author(s):

Lucie Nurdin ◽

Yan Yang ◽

Peter Neate ◽

Warren Piers ◽

Laurent Maron ◽

...

Keyword(s):

Room Temperature ◽

Ammonia Oxidation ◽

Important Process ◽

Hydrogen Atoms ◽

Ammine Complexes ◽

Ammonia Complex ◽

Aminyl Radical ◽

High Degree ◽

Radical Character ◽

We report the use of electron rich iron complexes supported by a dianionic diborate pentadentate ligand system, B2Pz4Py, for the coordination and activation of ammonia (NH3) and hydrazine (NH2NH2). For ammonia, coordination to neutral (B2Pz4Py)Fe(II) or cationic [(B2Pz4Py)Fe(III)]+ platforms leads to well characterized ammine complexes from which hydrogen atoms or protons can be removed to generate, fleetingly, a proposed (B2Pz4Py)Fe(III)- NH2 complex (3Ar-NH2). DFT computations suggest a high degree of spin density on the amido ligand, giving it significant aminyl radical character. It rapidly traps the H atom abstracting agent 2,4,6-tri-tert-butylphenoxy radical (ArO•) to form a C-N bond in a fully characterized product (2Ar), or scavenges hydrogen atoms to return to the ammonia complex (B2Pz4Py)Fe(II)-NH3 (1ArNH3). Interestingly, when (B2Pz4Py)Fe(II) is reacted with NH2NH2, a fully characterized bridging diazene complex, 4Ar, is formed along with ammonia adduct 1Ar-NH3 as the spectroscopically observed (-78˚C) (B2Pz4Py)Fe(II)-NH2NH2-Fe(II)( B2Pz4Py) dimer (1Ar)2-NH2NH2 is allowed to warm to room temperature. Experimental and computational evidence is presented to suggest that (B2Pz4Py)Fe(II) induces reductive cleavage of the N-N bond in hydrazine to produce the Fe(III)-NH2 complex 3Ar-NH2, which abstracts H• atoms from (1Ar)2-NH2NH2 to generate the observed products. All of these transformations are relevant to proposed steps in the ammonia oxidation reaction, an important process for the use of nitrogen-based fuels enabled by abundant first row transition metals.