Solvent‐Dependent Reversible Ligand Exchange in Nickel Complexes of a Monosulfide Bis(diphenylphosphino)(<i>N</i>‐thioether)amine

Ghisolfi, Alessio; Fliedel, Christophe; Rosa, Vítor; Pattacini, Roberto; Thibon, Aurore; Monakhov, Kirill Yu.; Braunstein, Pierre

doi:10.1002/asia.201300687

Cited by 26 publications

(54 citation statements)

References 70 publications

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“…The presence of these peaks indicates the presence of CAA and ZAA, which might be dissociated from the Z 0.7 C 0. 3 can be studied by XPS in Fig. 8.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and characterization of bis (acetylacetonato κ-O, O′) [zinc(ii)/copper(ii)] hybrid organic–inorganic complexes as solid metal organic precursors

et al. 2015

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We have synthesized novel metal organic hybrid mixed compounds of bis (acetylacetonato κ-O, O') [zinc(ii)/copper(ii)]. Taking C10H14O4Zn0.7Cu0.3 (Z0.7C0.3AA) as an example, the crystals are composed of Z0.7C0.3AA units and uncoordinated water molecules. Single-crystal X-ray diffraction results show that the complex Z0.7C0.3AA crystallizes in the monoclinic system, space group P21/n. The unit cell dimensions are a = 10.329(4) Å, b = 4.6947(18) Å, and c = 11.369(4) Å; the angles are α = 90°, β = 91.881(6)°, and γ = 90°, the volume is 551.0(4) Å(3), and Z = 2. In this process, the M(ii) ions of Zn and Cu mix and occupy the centers of symmetrical structural units, which are coordinated to two ligands. The measured bond lengths and angles of O-M-O vary with the ratio of metal species over the entire series of the complexes synthesized. The chemistry of the as-synthesized compounds has been characterized using infrared spectroscopy, mass spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis, and the morphology of the products has been characterized using scanning electron microscopy. The thermal decomposition of the Z0.7C0.3AA composites measured by thermogravimetric analysis suggests that these complexes are volatile. The thermal characteristics of these complexes make them attractive precursors for metal organic chemical vapor deposition.

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“…The presence of these peaks indicates the presence of CAA and ZAA, which might be dissociated from the Z 0.7 C 0. 3 can be studied by XPS in Fig. 8.…”

Section: Resultsmentioning

confidence: 99%

“…The υC=O mode appears at 1597, 1578, and 1600 cm -1 for ZAA, CAA, and Z 0.7 C 0.3 AA, respectively. The FT-IR spectra of ZAA, CAA, and Z 0.7 C 0 3. AA powders all show two 85 composite peaks in the 1250-1600 cm −1 region, assigned to the C-O-M bonds.…”

mentioning

confidence: 98%

Synthesis and characterization of bis (acetylacetonato κ-O, O′) [zinc(ii)/copper(ii)] hybrid organic–inorganic complexes as solid metal organic precursors

et al. 2015

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“…Ligand exchange is an important transformation in inorganic and organometallic chemistry and a critical step in many catalytic processes . Many ligand exchange processes can be induced by stoichiometric or catalytic electron‐transfer .…”

Section: Methodsmentioning

confidence: 99%

Reversible Electropolymerization of Nickel Complexes Based on Redox‐Mediated Ligand Exchange

et al. 2016

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Controlled and reversible ligand exchange reactions are useful tools for modulating reactivity of transition metal complexes. Here, we present a reversible electropolymerization of nickel azopyridine (azpy) complexes based on the redox-controlled diimine ligand exchange reaction. Upon a single electron reduction, (azpy)NiBr 2 disproportionates to afford (azpy) 2 Ni and a [NiBr 4 ] 2À , while in situ 1e À oxidation of this mixture leads to complete restoration of the original complex. Reversible intermetallic ligand exchange is also demonstrated between nickel and cobalt or iron azopyridine complexes. This facile and quantitative ligand exchange reaction was utilized to develop a reversible electropolymerization strategy to generate nickel metallopolymers containing redox-active azobispyridine ligands.Ligand exchange is an important transformation in inorganic and organometallic chemistry and a critical step in many catalytic processes. [1][2][3] Many ligand exchange processes can be induced by stoichiometric or catalytic electron-transfer. [4][5][6][7] Herein, we report a reversible electropolymerization based on redox-induced ligand exchange reaction using nickel complexes with azopyridine ligands [8,9] and the use of this strategy for the reversible redox-controlled synthesis of nickel metallopolymers. [10][11][12][13] Metallopolymers have elicited significant interest as materials for electrochromics, sensors, energy storage, and catalysis. [10][11][12][13][14][15][16][17][18][19][20][21] The dimeric nickel(II) complex [(mazpy)NiBr 2 ] 2 , 1, was prepared by treating (DME)NiBr 2 (DME = dimethoxyethane) with one equivalent of the methyl azopyridine ligand (mazpy) at 25 8C in methylene chloride. The 1 H NMR spectrum of 1 reveals strongly paramagnetically-shifted resonances consistent with a high-spin nickel(II). [22] The solid-state structure of 1 reveals a bromide-bridged dimer with distorted trigonal-bipyramidal coordination geometry at nickel (See Supporting Information). Re-duction of the dimeric complex, 1 with 2 equivalents of cobaltocene (CoCp 2 , 1 equiv. per nickel) immediately leads to the formation of a diamagnetic product, characterized as (mazpy) 2 Ni, 2, and [CoCp 2 ] 2 [NiBr 4 ] 2À (Scheme 1). The identity of 2 was confirmed by independent synthesis from Ni(cod) 2 (cod = 1,5cyclooctadiene) and two equivalents of the azopyridine ligand in dichloromethane (DCM) (page S13-15 in SI). [23] The reduction behavior of the dimeric complex 1 differs from that of a similar compound, monomeric (azpy) 2 NiCl 2 , which generates (azpy) 2 Ni upon 2e À reduction. [23] This redox-mediated ligand exchange reaction is fully reversible: re-oxidation of the mixture of 2 and [CoCp 2 ] 2 [NiBr 4 ] 2À or 2 and [NBu 4 ] 2 [NiBr 4 ] 2À with [Fc][BF 4 ]([Fc][BF 4 ] = ferrocenium tetrafluoroborate) regenerates the dimeric [(mazpy)NiBr 2 ], 1 quantitatively (Scheme 1b, page S23-26 in Supporting Information).This process can also be monitored by cyclic voltammetry (CV, Figure 1). The CV of 1 exhibits a cathodic reduction peak ...

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“…Greenish crystals of 2 were obtained after one week in moderate yield of 37.6 %. The positive ion-mode ESI mass spectrum of a MeOH:MeCN solution (volume ratio 1:1) of 1 reveals the molecular mass peak of the [Cu(HL·S) 2 this complex. Due to its polymeric nature and poor solubility 2 was not investigated by ESI mass spectrometry.…”

Section: Synthesis and Stability Of 1 Andmentioning

confidence: 99%

Ion‐Directed Coordinative Polymerization of Copper(II) Pyridyl‐Alcohol Complexes Through Thiane Functionalities

Schmitz

Izarova

Besson

et al. 2019

Zeitschrift anorg allge chemie

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A mononuclear complex [Cu(HL·S)2(NO3)2] (1) and a one‐ dimensional coordination polymer [Cu(HL·S)Cl2]n (2) [HL·S = 4‐(pyridin‐2‐ylmethyl)tetrahydro‐2H‐thiopyran‐4‐ol] showcase the structure‐directing role of the counterions in their formation reaction: monodentate ligation of NO3– and Cl– induces an octahedral (with two HL·S per Cu in 1) or trigonal‐bipyramidal (with one HL·S per Cu in 2) CuII coordination environment. In contrast to 1 exhibiting no coordinative metal–sulfur bonds in the crystal lattice (space group P21/c), 2 (P21/c) features intermolecular Cu–S contacts of 2.3188(7) Å. The coordination compounds are thermally stable up to ca. 160 °C. Whereas 1 demonstrates the spin‐like behavior of an isolated central CuII ion, compound 2 exhibits weak antiferromagnetic intra‐chain coupling with J ≈ –2.1 cm–1 between neighboring CuII ions.

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Solvent‐Dependent Reversible Ligand Exchange in Nickel Complexes of a Monosulfide Bis(diphenylphosphino)(N‐thioether)amine

Cited by 26 publications

References 70 publications

Synthesis and characterization of bis (acetylacetonato κ-O, O′) [zinc(ii)/copper(ii)] hybrid organic–inorganic complexes as solid metal organic precursors

Synthesis and characterization of bis (acetylacetonato κ-O, O′) [zinc(ii)/copper(ii)] hybrid organic–inorganic complexes as solid metal organic precursors

Reversible Electropolymerization of Nickel Complexes Based on Redox‐Mediated Ligand Exchange

Ion‐Directed Coordinative Polymerization of Copper(II) Pyridyl‐Alcohol Complexes Through Thiane Functionalities

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