Nickel(II) Aqua Complexes with Chelating Ligands: What Happens When Water Is Gone?

Opalade, Adedamola A.; Labádi, I.; Gómez‐García, Carlos J.; Hietsoi, Oleksandr; Gerasimchuk, Nikolay

doi:10.1021/acs.cgd.2c00717

Cited by 5 publications

(5 citation statements)

References 46 publications

(71 reference statements)

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“…This is consistent with several similar geometries we have recently observed in Pt(II) complexes with cyanoximes [38][39][40]. This is different from numerous trans complexes of cyanoximes with light transition metals of 3d series: Ni 2+ [41], Cu 2+ [42,43],…”

Section: Crystal Structuressupporting

confidence: 91%

Synthesis and Characterization of Pt(II) and Pd(II) Complexes with Planar Aromatic Oximes

et al. 2023

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A series of four Werner-type complexes of Pd(II) and Pt(II) with planar, isomeric conjugated aromatic naphtoquinone oximes were synthesized for the first time. These ligands were 1-oxime-2-naphtoquinone (HL1) and 2-oxime-1-napthoquinone (HL2). Compounds were characterized using thermal analysis, spectroscopic methods, and X-ray analysis. TG/DSC data were collected for pure starting organic ligands, their complexes, and indicated vigorous exothermic decomposition with at ~155 °C for starting HL and ~350 °C for transition metal complexes. Crystal structures for two Pt compounds with 2-oxime-1-quinone were determined and revealed the formation of the cis-geometry complexes and incorporation of molecules of stoichiometric solvents in the lattice: acetonitrile and nitrobenzene. Both solvents of crystallization displayed attractive interactions between their C-H groups and the oxygen atoms of the nitroso groups in complexes, leading to short distances in those fragments. Despite the presence of solvents of inclusion, the overall structure motifs in both compounds represent 1D columnar coordination polymer, in which the PtL2 units are held together via metallophilic interactions, thereby forming ‘Pt-wires’. The Hirshfield surface analysis was performed for both crystallographically characterized complexes. The results showed intermolecular π–π stacking and Pt–Pt interactions among the planar units of both complexes. In addition, the analysis also verified the presence of hydrogen bonding interactions between the platinum unit and solvent molecules. Solid bulk powdery samples of both PtL12 and PtL22 demonstrated pronounced photoluminescence in the near infrared region of spectrum at ~980 nm, being excited in the range of 750–800 nm. The NIR emission was observed only for Pt-complexes and not for pure starting organic ligands or Pd-complexes. Additionally, synthesized Pt-naphtoquinone oximes do not show luminescence in solutions, which suggests the importance of a 1D ‘metal wire’ structure for this process.

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Section: Crystal Structuressupporting

confidence: 91%

Synthesis and Characterization of Pt(II) and Pd(II) Complexes with Planar Aromatic Oximes

et al. 2023

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“…The channels in the latter can accommodate columns of Br or I atoms, leading to the charge transfer inclusion type complexes, where the Ni–Ni distance is lowered to 3.271(1) Å at ambient temperature [ 27 ], or to 3.223(2) Å at −160 °C [ 29 ]. A recent review of Ni complexes that form 1D stacks in which metal centres are directly aligned because of metallophilic interactions is provided in [ 30 ].…”

Section: Discussionmentioning

confidence: 99%

Old Acquaintances and Novel Complex Structures for the Ni(II) and Cu(II) Complexes of bis-Chelate Oxime–Amide Ligands

Bazzicalupi,

Grimmer,

Nikolayenko

2024

Molecules

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In the process of systematically studying the methylhydroxyiminoethaneamide bis-chelate ligands with polymethylene spacers of different lengths, L1–L3, and their transition metal complexes, a number of new Ni(II) and Cu(II) species have been isolated, and their molecular and crystal structures were determined using single-crystal X-ray diffraction. In all of these compounds, the divalent metal is coordinated by the ligand donor atoms in a square-planar arrangement. In addition, a serendipitously discovered new type of neutral Ni(II) complex, where the propane spacer of ligand L2 underwent oxidation to the propene spacer, and one of the amide groups was oxidised to the ketoimine, is also reported. The resulting ligand L2′ affords the formation of neutral planar Ni(II) complexes, which are assembled in the solid state on top of each other, and yield two polymorphic structures. In both structures, the resulting infinite, exclusively parallel metal ion columns in ligand insulation may serve as precursor materials for sub-nano-conducting connectors. Overall, this paper reports the synthesis and characterisation of seven new anionic, cationic, and neutral Ni(II) and Cu(II) complexes, their crystal structures, as well as experimental and computed UV–Vis absorption spectra for two structurally similar Ni(II) complexes, yellow and red.

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“…This square-planar n d 8 electronic configuration is low-spin diamagnetic with the preferred square planar geometry around the metal centers. Such complexes of metals ions of the Ni-triad also demonstrate a strong propensity for the formation of dimers (Chart B) and one-dimensional structures in which metal centers are directly aligned due to metallophilic interactions of different strengths (Chart C). , If coordinated to the metal center (herein specifically to Ni), ligands can perform a bridging function, and then a distorted “ladder-type” chain of hexacoordinated complexes is formed (Chart D) . In cases B–D as in Chart , the aggregation is the driving force facilitating these structural motifs. , The most interesting cases include the tetracyanoplatinates M′ 2 [Pt(CN) 4 ], M″[Pt(CN) 4 ] (M′ = Li – Cs; M″ = Mg – Ba); − Magnus Green Salt (MGS) [Pt(NH 3 ) 4 ][PtCl 4 ]; and Beckton and Millon salts .…”

Section: Introductionmentioning

confidence: 99%

“…Inorganic, organometallic, and Werner-type coordination chemistry of nickel is particularly well developed with chelating ligands. − However, with the exception of only a few publications, , not much is generally known about complexes of Ni(II) with cyanoximes. The latter were established to be excellent ampolydentate ligands .…”

Section: Introductionmentioning

confidence: 99%

“…2,3 If coordinated to the metal center (herein specifically to Ni), ligands can perform a bridging function, and then a distorted "ladder-type" chain of hexacoordinated complexes is formed (Chart 1D). 4 In cases B−D as in Chart 1, the aggregation is the driving force facilitating these structural motifs. 5,6 The most interesting cases include the tetracyanoplatinates M′ 2 [Pt(CN) 4 ], M″[Pt(CN) 4 ] (M′ = Li − Cs; M″ = Mg − Ba); 7−9 Magnus Green Salt (MGS) [Pt(NH 3 ) 4 ][PtCl 4 ]; 10 and Beckton and Millon salts.…”

Section: ■ Introductionmentioning

confidence: 99%

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Remarkable Structural Diversity of N-Pyrrolidine-cyanoxime and its Ni(II) Complexes

Opalade,

Gerasimchuk,

Hietsoi

et al. 2024

Crystal Growth & Design

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A novel cyanoxime, 2-oximino-2-cyano-N-pyrrolidine-acetamide (further HPyrCO), was synthesized and characterized by spectroscopic methods, thermal analysis, and X-ray crystallography. The structure revealed eight independent molecules with elaborate intermolecular H-bonding in the asymmetric unit and adoption of the trans-anti configuration of the cyanoxime. Henceforth, a series of Ni(II) coordination compounds, crystallohydrates, with this new cyanoxime was obtained from aqueous solutions, with four complexes isolated from the same system after filtration of the main product and subsequent crystallization of new products from the mother liquor. These were RED, the main productouter-sphere solvent molecules of crystallization and were obtained as the result of direct interaction of starting compounds in narrow tubes. All isolated complexes were characterized using IR, solid-state UV−visible spectroscopy, TG/DSC analysis, and X-ray crystallography. Data showed the formation of five-membered chelate rings in all structures and adoption of the trans-geometry of cyanoxime in all crystallohydrate complexes. Heating of the RED, GREEN, and VIOLET crystallohydrates led to irreversible dehydration and the formation of an anhydrous brown complex, [Ni(PyrCO) 2 ]. Variable temperature magnetochemical studies of RED trihydrate confirmed a lack of interactions between isolated Ni(II) centers, while there was an antiferromagnetic interaction between metal ions in the linear chain in the polymeric anhydrous compound. Full line shape analysis of solid-state electronic spectra allowed calculation of the Racah Repulsion Parameter (B) and Nephelauxetic Constant (β). In three crystallohydrates, there were six-coordinated high-spin Ni 2+ complexes with different degrees of rhombic (with axial elongation) distortions and, therefore, ligands' crystal field strength. The final product of the thermal decomposition of all complexes under inert gas protection was metallic Ni sponge.

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Nickel(II) Aqua Complexes with Chelating Ligands: What Happens When Water Is Gone?

Cited by 5 publications

References 46 publications

Synthesis and Characterization of Pt(II) and Pd(II) Complexes with Planar Aromatic Oximes

Synthesis and Characterization of Pt(II) and Pd(II) Complexes with Planar Aromatic Oximes

Old Acquaintances and Novel Complex Structures for the Ni(II) and Cu(II) Complexes of bis-Chelate Oxime–Amide Ligands

Remarkable Structural Diversity of N-Pyrrolidine-cyanoxime and its Ni(II) Complexes

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