Displacement of triphenylphosphine from Cu(PPh3)2NO3 and Co(PPh3)2Cl2 by a diselenoimidodiphosphinato ligand. X-ray crystal structure of (PPh3)Cu[Ph2P(Se)NP(Se)Ph2] and Co[Ph2P(Se)NP(Se)Ph2]2 containing the novel CuSe2P2N and CoSe2P2N inorganic metallocycles

Novosad, Josef; Nečas, Marek; Marek, Jaromı́r; Veltsistas, Panayotis G.; Papadimitriou, Christos; Haiduc, Ionel; Watanabe, Makoto; Woollins, J. Derek

doi:10.1016/s0020-1693(99)00154-1

Cited by 39 publications

(19 citation statements)

References 43 publications

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“…Additionally, the resonances of protons for coordinated THF molecules appeared at δ = 3.57 and 1.33 ppm as multiplets, and these values are in the expected range. The proton decoupled 31 P{ 1 H} NMR spectrum showed only one doublet at δ = 55.9 ppm which was up-field shifted compared to the corresponding value in 1-H (δ = 65.6 ppm). A doublet The lithium complex 2 was re-crystallized from THF/pentane (1:2) and crystallized in orthorhombic space group Pca2 1 having four molecules in the unit cell.…”

Section: Lithium Complexmentioning

confidence: 92%

“…Complex 2 was fully characterized by combustion analysis and 1 H, 31 P{ 1 H}, and 11 B{ 1 H} NMR spectroscopic technique. The molecular structure in the solid state of the complex 2 was determined by single-crystal X-ray diffraction analysis.…”

Section: Lithium Complexmentioning

confidence: 99%

“…[11,12] The di-chalcogenoimido-diphosphinto bismuth compounds, Bi[(EPR 2 ) 2 N] 3 (E = S, Se; R = Ph, iPr), were found to be ideal www.zaac.wiley-vch.de ARTICLE for use as single-source precursors as they are air-stable and readily obtainable in good synthetic yields. [13] The diselenoimido-diphosphinato ligand can also stabilize a wide range of metal coordination spheres including alkali metals, [14][15] group 12, [16] group 13, [17,18] group 14, [19,20,16] group 15, [21] group 16, [22,23] transition metals (V and Cr, [24] Mn [25,26] and Re, [27] Ru, Rh, Ir, [15,28,29] Os, [30] Co, [31] group 10: Ni, [32] Pd, [32,[33][34][35] Pt, [14,30,34] and group 11: [35] , and rare earth metals. [36,37] This could be due to the flexible nature of the ligand moieties, which adopt to several metallacyclic rings depending upon the coordination to the central metal atom.…”

Section: Introductionmentioning

confidence: 99%

“…The ligand 1-H was re-crystallized from hexane and was fully characterized by using spectroscopic and analytical techniques. The 1 H, 31 P{ 1 H}, and 11 B{ 1 H} NMR spectra showed one set of signals for 1-H. The resonances for the BH 3 protons appeared as a broad signal at δ = 1.86 ppm.…”

mentioning

confidence: 99%

“…The resonance of the NH proton could be observed as a singlet at δ = 4.46 ppm. In the 31 P{ 1 H} spectrum of 1-H, a doublet signal at δ = 65.6 ppm was observed. The boron atoms present in 1-H showed a doublet resonance centered at δ -35.9 ppm in 11 B{ 1 H} spectrum.…”

mentioning

confidence: 99%

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Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Bhattacharjee

Das

Reddy

et al. 2015

Zeitschrift anorg allge chemie

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Abstract. The syntheses of lithium and alkaline earth metal complexes with the bis(borane-diphenylphosphanyl)amido ligand (1-H) of molecular formulas [{κ 2 -N(PPh 2 (BH 3 )) 2 }Li(THF) 2 ] (2) and (3), Sr (4), Ba (5)] are reported. The lithium complex 2 was obtained by treatment of bis(borane-diphenylphosphanyl)amine (1-H) with lithium bis(trimethylsilyl)-amide in a 1:1 molar ratio via the silylamine elimination method. The corresponding homoleptic alkaline earth metal complexes 3-5 were prepared by two synthetic routes -first, the treatment of metal bis(trimethylsilyl)amide and protio ligand 1-H via the elimination of silylamine, and second, through salt metathesis reaction involving respective metal diiodides and lithium salt 2. The molecular structures of lithium complex 2 and barium complex 5 were established by

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Section: Lithium Complexmentioning

confidence: 92%

Section: Lithium Complexmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Bhattacharjee

Das

Reddy

et al. 2015

Zeitschrift anorg allge chemie

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Magnetic Anisotropy in Co^IIX₄ (X=O, S, Se) Single‐Ion Magnets: Role of Structural Distortions versus Heavy Atom Effect

Sarkar

Tewary

Sinkar

et al. 2019

Chemistry An Asian Journal

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Mononuclearf our coordinate Co II complexes have drawn ag reat deal of attention as they often exhibit excellent single-ion magnet (SIM) properties. Among the reported complexes, the axial zero-field splitting parameter (D)w as found to vary drastically both in terms of the sign as well as strength. There are variousp roposals in this respects uch as structural distortions,h eaviera tom substitution, metalligand covalency,t uning secondary coordination sphere, etc. that are expected to control the D values. To assess the importance of structurald istortions vs. heaviera tom substitution effect, herew eh ave undertaken detailed theoretical studies based on the ab initio CASSCF/NEVPT2 methodt o estimate zero-field splitting parameters for twelve complexes reported in the literature. Our test set includes the {Co II X 4 } (where X = O, S, Se) core structure where the D value was found to vary from + 19 to À118cm À1 .B ased on the structural variation, we have classified the complexes into three types (I-III)w here type I complexes were found to exhibit the largestn egative D value as desired for SIMs. The other two types (II and III)o fc omplexes have been found to be inferior with respect to type I. The secondary coordination spherew as also found to influence D,a ss ubstitution on the secondary coordination sphere atom was found to significantly alter the magnitude of D values. Particularly,t wo structuralp arameters, namely,t he dihedrala ngle between the two ligand planes and the ffX-Co-X polar angle were found to heavily influence the sign and strength of D values. Our analysis clearly reveals that these structural factors are much more important than the heavier atom substitution,o r metal-ligand covalency.Alarge variation in the D and E/D values among these complexesd espite possessing av ery close structuralsimilarity offers an exquisite playground for a chemistt odesign and develop new-generation Co II -based SIMs.

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The [Fe{(SePPh₂)₂N}₂] Complex Revisited: X‐ray Crystallography, Magnetometry, High‐Frequency EPR, and Mössbauer Studies Reveal Its Tetrahedral Fe^IISe₄ Coordination Sphere

et al. 2018

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The synthesis and characterization of complex [Fe{(SePPh 2 ) 2 N} 2 ] (1) is described. X-ray crystallography shows that this system contains a tetrahedral FeSe 4 coordination sphere. The structural features of 1 are compared with those of similar first row transition element complexes, including a recently reported preparation of [Fe{(SePPh 2 ) 2 N} 2 ] (1 SP ) exhibiting a highly unusual square planar FeSe 4 coordination sphere. The [a] 713 electronic structure of 1 was elucidated by magnetometry, high-frequency EPR, and Mössbauer spectroscopic studies, which reveal zero-field splitting (ZFS) parameters typical of high spin S = 2 tetrahedral Fe II sites. Accurate ZFS parameters (D = +8.22 cm -1 , E/D = 0.104) were obtained by analysis of the EPR spectra and compared with those of the analogous [Fe{(SPPh 2 ) 2 N} 2 ] complex.its active site have been investigated. [6] The effects of replacing Cys by Se-Cys have been investigated in various metalloproteins, such as metallothionein, [7] Cyt P 450 , [8] azurin, [9] and sulfite oxidase. [10] Moreover, sulfide S 2has been replaced by selenide Se 2in the iron-sulfur active site of numerous proteins, [11] like the [4Fe-4S] cluster of [FeFe]-hydrogenase [12a] (Se/S substitution has also been carried out in the [2Fe] cluster of the latter [12b] ), the iron protein of nitrogenase, [13] the photosystem I polypeptide PsaC, [14] aconitase, [15] high potential ironsulfur protein, [16] as well as [2Fe-2S] [17] and 2[4Fe-4S] ferredoxins. [18] As far as the synthetic bioinorganic chemistry of selenium is concerned, a range of multinuclear clusters containing iron coordinated to Se 2and various thiols, [19] as well as tungsteniron-sulfur/selenium clusters, [20] have been investigated by Holm and co-workers. The coordination of selenium to transition metals has also been explored by employing the so called dichalcogenidoimidodiphosphinato ligands, R 2 P(E)NHP(E′)R′ 2 (E, E′ = O, S, Se, Te; R, R ′ = alkyl or aryl groups). [21] Among this family of chelating ligands, L = [Ph 2 P(Se)NP(Se)Ph 2 ] -, [22] containing E = E′ = Se as donor atoms, and R = R′ = Ph as peripheral groups bonded to the P atoms of the P-N-P backbone, has afforded the following structurally characterized homoleptic complexes with first series transition metal ions (structures deposited in the Cambridge Structural Database, CSD [23] ): octahedral M III L 3 , M = V, [24] Cr, [24] tetrahedral M II L 2 , M = Mn, [25] Co, [26] Zn, [27] square planar Ni II L 2 [28] and tetranuclear [Cu I 4 L 3 ]BF 4 . [29] With respect to the coordination of [Ph 2 P(Se)NP(Se)Ph 2 ]to Fe II , it should first be noted that the following literature complexes have been shown, by X-ray crystallography, to unequivocally contain a tetrahedral FeSe 4 coordination sphere: [N(CH 3 CH 2 ) 4 ] 2 [Fe(SePh) 4 ], [30] [Fe(1,10-phen) 3 ][Fe(SePh) 4 ], [31] Eur. J. Inorg. Chem. 2018, 713-721 www.eurjic.org

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Displacement of triphenylphosphine from Cu(PPh3)2NO3 and Co(PPh3)2Cl2 by a diselenoimidodiphosphinato ligand. X-ray crystal structure of (PPh3)Cu[Ph2P(Se)NP(Se)Ph2] and Co[Ph2P(Se)NP(Se)Ph2]2 containing the novel CuSe2P2N and CoSe2P2N inorganic metallocycles

Cited by 39 publications

References 43 publications

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Magnetic Anisotropy in Co^IIX₄ (X=O, S, Se) Single‐Ion Magnets: Role of Structural Distortions versus Heavy Atom Effect

The [Fe{(SePPh₂)₂N}₂] Complex Revisited: X‐ray Crystallography, Magnetometry, High‐Frequency EPR, and Mössbauer Studies Reveal Its Tetrahedral Fe^IISe₄ Coordination Sphere

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Displacement of triphenylphosphine from Cu(PPh3)2NO3 and Co(PPh3)2Cl2 by a diselenoimidodiphosphinato ligand. X-ray crystal structure of (PPh3)Cu[Ph2P(Se)NP(Se)Ph2] and Co[Ph2P(Se)NP(Se)Ph2]2 containing the novel CuSe2P2N and CoSe2P2N inorganic metallocycles

Cited by 39 publications

References 43 publications

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Alkali Metal and Alkaline Earth Metal Complexes with the Bis(borane‐diphenylphosphanyl)amido Ligand – Synthesis, Structures, and Catalysis for Ring‐Opening Polymerization of ϵ‐Caprolactone

Magnetic Anisotropy in CoIIX4 (X=O, S, Se) Single‐Ion Magnets: Role of Structural Distortions versus Heavy Atom Effect

The [Fe{(SePPh2)2N}2] Complex Revisited: X‐ray Crystallography, Magnetometry, High‐Frequency EPR, and Mössbauer Studies Reveal Its Tetrahedral FeIISe4 Coordination Sphere

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Magnetic Anisotropy in Co^IIX₄ (X=O, S, Se) Single‐Ion Magnets: Role of Structural Distortions versus Heavy Atom Effect

The [Fe{(SePPh₂)₂N}₂] Complex Revisited: X‐ray Crystallography, Magnetometry, High‐Frequency EPR, and Mössbauer Studies Reveal Its Tetrahedral Fe^IISe₄ Coordination Sphere