[(TMEDA)Co(NO)2][BPh4]: A versatile synthetic entry point to four and five coordinate {Co(NO)2}10 complexes

Crimmin, Mark R.; Rosebrugh, Lauren E.; Tomson, Neil C.; Weyhermüller, Thomas; Bergman, Robert G.; Toste, F. Dean; Wieghardt, Karl

doi:10.1016/j.jorganchem.2011.04.038

Cited by 14 publications

(14 citation statements)

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“…Therefore, [Co(NO) 2 (L1")](BF 4 ) is diamagnetic. This diamagnetic magnetic property of other {Co(NO) 2 } 10 dinitrosyl complexes is observed in (Et 4 N)[Co(NO) 2 (SPh) 2 ] [40], [Co(NO) 2 (Ar-nacnac)] [23], and [Co(NO) 2 (tmeda)](BPh 4 ) [33,41]. The origin of this diamagnetism has not been noted, to our best knowledge.…”

Section: Magnetic Propertymentioning

confidence: 61%

“…In the dinitrosyl cobalt complexes, the {Co(NO) 2 } 10 oxidation state is commonly encountered, as listed in Table 2 [23,33,[39][40][41][42][43]. Regarding the electronic structure of {Co(NO) 2 } core in the complexes, the reported {Co(NO) 2 } 10 core is of diamagnetic property (S t = 0) [23,33,40,41]. Moreover, there is the relatively wide range ν(N-O) frequency from 1900 cm −1 to 1700 cm −1 [23,39,40].…”

Section: Introductionmentioning

confidence: 99%

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Structures and Properties of Dinitrosyl Iron and Cobalt Complexes Ligated by Bis(3,5-diisopropyl-1-pyrazolyl)methane

2019

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Two dinitrosyl iron and cobalt complexes [Fe(NO)2(L1”)](BF4) and [Co(NO)2(L1”)](BF4) are synthesized and characterized, supported by a less hindered bidentate nitrogen ligand bis(3,5-diisopropyl-1-pyrazolyl)methane (denoted as L1”), are surprisingly stable under argon atmosphere. X-ray structural analysis shows a distorted tetrahedral geometry. Spectroscopic and structural parameters of the dinitrosyl iron and cobalt complexes are consistent with the previous reported {Fe(NO)2}9 and {Co(NO)2}10. Two N–O and M–N(O) stretching frequencies and their magnetic properties are also consistent with the above electronic structural assignments. We explored the dioxygen reactivities of the obtained dinitrosyl complexes. Moreover, the related [FeCl2(L1”)], [Co(NO3)2(L1”)], and [Co(NO2)2(L1”)] complexes are also characterized in detail.

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Section: Magnetic Propertymentioning

confidence: 61%

Section: Introductionmentioning

confidence: 99%

Structures and Properties of Dinitrosyl Iron and Cobalt Complexes Ligated by Bis(3,5-diisopropyl-1-pyrazolyl)methane

2019

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“…After reporting different reduced products for bis(oxyanion) complexes coordinated to iron and nickel, we were interested in the reductive deoxygenation of a cobalt complex bearing two nitrogen oxyanion ligands. We hypothesized that the formation of a cobalt dinitrosyl complex was possible; however, most reported Co(NO) 2 complexes with neutral ancillary donors are monocationic to invoke {Co(NO) 2 } in the Enemark–Feltham notation. − …”

Section: Resultsmentioning

confidence: 99%

An Integrated View of Nitrogen Oxyanion Deoxygenation in Solution Chemistry and Electrospray Ion Production

et al. 2021

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There has been an increasing interest in chemistry involving nitrogen oxyanions, largely due to the environmental hazards associated with increased concentrations of these anions leading to eutrophication and aquatic “dead zones”. Herein, we report the synthesis and characterization of a suite of MNO x complexes (M = Co, Zn: x = 2, 3). Reductive deoxygenation of cobalt bis(nitrite) complexes with bis(boryl)pyrazine is faster for cobalt than previously reported nickel, and pendant O-bound nitrito ligand is still readily deoxygenated, despite potential implication of an isonitrosyl primary product. Deoxygenation of zinc oxyanion complexes is also facile, despite zinc being unable to stabilize a nitrosyl ligand, with liberation of nitric oxide and nitrous oxide, indicating N–N bond formation. X-ray photoelectron spectroscopy is effective for discriminating the types of nitrogen in these molecules. ESI mass spectrometry of a suite of M(NO x ) y (x = 2, 3 and y = 1, 2) shows that the primary form of ionization is loss of an oxyanion ligand, which can be alleviated via the addition of tetrabutylammonium (TBA) as a nonintuitive cation pair for the neutral oxyanion complexes. We have shown these complexes to be subject to deoxygenation, and there is evidence for nitrogen oxyanion reduction in several cases in the ESI plume. The attractive force between cation and neutral is explored experimentally and computationally and attributed to hydrogen bonding of the nitrogen oxyanion ligands with ammonium α-CH2 protons. One example of ESI-induced reductive dimerization is mimicked by bulk solution synthesis, and that product is characterized by X-ray diffraction to contain two Co(NO)2 + groups linked by a highly conjugated diazapolyene.

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“…It was noticed that the IR spectra of the six-coordinate, five-coordinate, and four-coordinate DNICs ([(NO) 2 FeL 2 ] (L=thiolate, imidazolate)) all had the same peak patterns but differed in the position of ν NO and the separation of q NO in the NO stretching frequencies (q NO , ~101 cm −1 for six-coordinate vs. ~73 cm −1 for five-coordinate vs. ~60–45 cm −1 for four-coordinate DNICs). Interestingly, several other 4 and 5 coordinate nitrosyl complexes have also been synthesized using cobalt instead of iron [56]. …”

Section: Dinitrosyl Complexes Containing a Single Metal Centermentioning

confidence: 99%

The Preparation, Structural Characteristics, and Physical Chemical Properties of Metal-Nitrosyl Complexes

Holloway

2013

Nitrosyl Complexes in Inorganic Chemistry, Biochemistry and Medicine II

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The preparation and characterization of a representative group of novel non-heme metal nitrosyl complexes that have been synthesized over the last decade are discussed here. Their structures are examined and classified based on metal type, the number of metal centers present, and the type of ligand that is coordinated with the metal. The ligands can be phosphorus, nitrogen, or sulfur based (with a few exceptions) and can vary depending on the presence of chelation, intermolecular forces, or the presence of other ligands. Structural and bonding characteristics are summarized and examples of reactivity regarding nitrosyl ligands are given. Some of the relevant physical chemical properties of these complexes, including IR, EPR, NMR, UV–vis, cyclic voltammetry, and X-ray crystallography are examined.

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[(TMEDA)Co(NO)2][BPh4]: A versatile synthetic entry point to four and five coordinate {Co(NO)2}10 complexes

Cited by 14 publications

References 62 publications

Structures and Properties of Dinitrosyl Iron and Cobalt Complexes Ligated by Bis(3,5-diisopropyl-1-pyrazolyl)methane

Structures and Properties of Dinitrosyl Iron and Cobalt Complexes Ligated by Bis(3,5-diisopropyl-1-pyrazolyl)methane

An Integrated View of Nitrogen Oxyanion Deoxygenation in Solution Chemistry and Electrospray Ion Production

The Preparation, Structural Characteristics, and Physical Chemical Properties of Metal-Nitrosyl Complexes

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