Synthesis and characterization of two novel cobalt (II) phosphine complexes: crystal structures of [CoCl3(Cy2PCH2PCy2H)] and [Co(NO3)2(Cy2PCH2PCy2O)]. Cy=cyclohexyl, C6H11

Kriley, Charles E.; Majireck, Max M.; Tobolewski, Jake M.; Kelvington, Luke E.; Cummings, Stephen H.; Hershberger, Stefan J.; Link, Jason D.; Silverio, Anthony L.; Fanwick, Phillip E.; Rothwell, Ian P.

doi:10.1016/j.ica.2004.06.063

Cited by 6 publications

(5 citation statements)

References 19 publications

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“…The long Co–O contacts are well within the sum of the van der Waals radii (3.44 Å). The bis(nitrate) is comparable to other cobalt bis(nitrate) complexes with two other ancillary donors. − Cobalt bis(nitrite) complexes are usually N-bound and six-coordinate, − and we hypothesize the nitrite ligands are O-bound in (DIM)Co(NO 2 ) 2 to accommodate bidentate binding and provide a six-coordinate environment about the cobalt center. The structure of the zinc bis(nitrate) has two bidentate nitrates, each with one long (2.22 Å) and one short (2.09 Å) Zn–O distance.…”

Section: Resultsmentioning

confidence: 72%

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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Section: Resultsmentioning

confidence: 72%

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

et al. 2021

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“…These bond parameters of 1 and 2 are comparable to those reported for the Co( ii ) complexes with a [CoPX 3 ] (X = Cl, Br) moiety. 58–64…”

Section: Resultsmentioning

confidence: 99%

“…These bond parameters of 1 and 2 are comparable to those reported for the Co(II) complexes with a [CoPX 3 ] (X = Cl, Br) moiety. [58][59][60][61][62][63][64] There is a C 3 axis going through the Co-P bond in the anions of molecules of 1 and 2, in which the [CoPX 3 ] − moiety possesses crystallographically imposed C 3v symmetry. Continuous shape measure (CShM) analyses with Shape 2.1 65,66 have been performed to evaluate the degree of deviation with respect to an ideal tetrahedron.…”

Section: Description Of the Crystal Structuresmentioning

confidence: 99%

Magnetic anisotropy of two tetrahedral Co(ii)-halide complexes with triphenylphosphine ligands

Cui

Chen

et al. 2022

Dalton Trans.

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“…Further attempts to prepare the diallyl complex using t BuLi as a base are currently in progress. The coordination chemistry of bis(dicyclohexylphosphino)methane (dcpm) has been explored to a far lesser extent than that of the related bis(diphenylphosphino)methane (dppm) [46,[74][75][76][77][78][79][80]. This is in part to its more challenging synthesis and air sensitivity in solution.…”

Section: Resultsmentioning

confidence: 99%

Backbone modified small bite-angle diphosphines: Synthesis and molecular structures of [M(CO)4{X2PC(R1R2)PX2}] (M=Mo, W; X=Ph, Cy; R1=H, Me, Et, Pr, allyl, R2=Me, allyl)

Hogarth¹,

Kilmartin²

2007

Journal of Organometallic Chemistry

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Synthesis and characterization of two novel cobalt (II) phosphine complexes: crystal structures of [CoCl3(Cy2PCH2PCy2H)] and [Co(NO3)2(Cy2PCH2PCy2O)]. Cy=cyclohexyl, C6H11

Cited by 6 publications

References 19 publications

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

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

Magnetic anisotropy of two tetrahedral Co(ii)-halide complexes with triphenylphosphine ligands

Backbone modified small bite-angle diphosphines: Synthesis and molecular structures of [M(CO)4{X2PC(R1R2)PX2}] (M=Mo, W; X=Ph, Cy; R1=H, Me, Et, Pr, allyl, R2=Me, allyl)

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