Search results for "TRANSITION"
showing 10 items of 3988 documents
Structural, photophysical and magnetic properties of transition metal complexes based on the dipicolylamino-chloro-1,2,4,5-tetrazine ligand
2015
International audience; The ligand 3-chloro-6-dipicolylamino-1,2,4,5-tetrazine (Cl-TTZ-dipica) 1, prepared by the direct reaction between 3,6-dichloro-1,2,4,5-tetrazine and di(2-picolyl)-amine, afforded a series of four neutral transition metal complexes formulated as [Cl-TTZ-dipica-MCl2]2, with M = Zn(II), Cd(II), Mn(II) and Co(II), when reacted with the corresponding metal chlorides. The dinuclear structure of the isostructural complexes was disclosed by single crystal X-ray analysis, clearly indicating the formation of [MII–(μ-Cl)2MII] motifs and the involvement of the amino nitrogen atom in semi-coordination with the metal centers, thus leading to distorted octahedral coordination geome…
An Entry to Mixed NHC-Fischer Carbene Complexes and Zwitterionic Group 6 Metal Alkenyls
2016
The addition of NHCs to α,β-unsaturated Cr(0) and W(0) (Fischer) carbene complexes is strongly dependent on the electrophilicity of the carbene carbon. Electrophilic alkoxy-carbene complexes quantitatively react with NHCs to yield stable zwitterionic (racemic) Cr(0) - and W(0) -alkenyls with total regio- and E-stereoselectivity. Less electrophilic aminocarbenes react with NHCs to promote the displacement of a CO ligand and yield "mixed" NHC/Fischer biscarbenes in a process that is unprecedented in group 6 metal-carbene chemistry. In fact, the compounds prepared, are some of the scarce examples of Fischer bisylidenes reported in the literature. The electrochemistry of the zwitterionic Cr(0) …
2015
Biphenols are important structure motifs for ligand systems in organic catalysis and are therefore included in the category of so-called "privileged ligands". We have developed a new synthetic pathway to construct these structures by the use of selenium dioxide, a stable, powerful, and commercially available oxidizer. Our new, and easy to perform protocol gives rise to biphenols and diaryl selenides depending on the solvent employed. Oxidative treatment of phenols in acetic acid yields the corresponding biphenols, whereas conversion in pyridine results in the preferred formation of diaryl selenides. As a consequence, we were able to isolate a broad scope of novel diaryl selenides, which cou…
2021
A nickel complex incorporating an N2 O ligand with a rare η2 -N,N'-coordination mode was isolated and characterized by X-ray crystallography, as well as by IR and solid-state NMR spectroscopy augmented by 15 N-labeling experiments. The isoelectronic nickel CO2 complex reported for comparison features a very similar solid-state structure. Computational studies revealed that η2 -N2 O binds to nickel slightly stronger than η2 -CO2 in this case, and comparably to or slightly stronger than η2 -CO2 to transition metals in general. Comparable transition-state energies for the formation of isomeric η2 -N,N'- and η2 -N,O-complexes, and a negligible activation barrier for the decomposition of the lat…
Interactions of a Diplumbyne with Dinuclear Transition Metal Carbonyls to Afford Metalloplumbylenes
2020
The metathesis reactions of the diplumbyne AriPr6PbPbAriPr6 (AriPr6 = −C6H3–2,6-(C6H2–2,4,6-iPr3)2) with the dinuclear metal carbonyls Mn2(CO)10, Fe2(CO)9, and Co2(CO)8 under mild conditions afforded the complexes Mn(CO)5(PbAriPr6) (1), Fe(CO)4(PbAriPr6)2 (2), and Co4(CO)9(PbAriPr6)2 (3), respectively. Complexes 1–3 were structurally characterized by single-crystal X-ray diffraction and spectroscopically characterized by 1H, 13C{1H}, 59Co{1H}, and 207Pb{1H} NMR; UV–vis; and IR methods. They are rare examples of species formed by the direct reaction of a group 14 dimetallyne with transition metal carbonyls. Complexes 1 and 2 feature Mn–Pb or Fe–Pb single bonds, whereas in 3 a Co–Pb cluster i…
Reappraising Schmidpeter's bis(iminophosphoranyl)phosphides: coordination to transition metals and bonding analysis
2020
The synthesis and characterization of a range of bis(iminophosphoranyl)phosphide (BIPP) group 4 and coinage metals complexes is reported. BIPP ligands bind group 4 metals in a pseudo fac-fashion, and the central phosphorus atom enables the formation of d0–d10 heterobimetallic complexes. Various DFT computational tools (including AIM, ELF and NCI) show that the phosphorus–metal interaction is either electrostatic (Ti) or dative (Au, Cu). A bridged homobimetallic Cu–Cu complex was also prepared and its spectroscopic properties were investigated. The theoretical analysis of the P–P bond in BIPP complexes reveals that (i) BIPP are closely related to ambiphilic triphosphenium (TP) cations; (ii) …
Light-Induced Alkylation of (Hetero)aromatic Nitriles in a Transition-Metal-Free C–C-Bond Metathesis
2017
A light-induced C–C-σ-bond metathesis was achieved through transition-metal-free activation of an unstrained C(sp3)–C(sp3)-σ-bond in 1-benzyl-1,2,3,4-tetrahydroisoquinolines. A photoredox-mediated single-electron oxidation of these precursor amines yield radical cations which undergo a homolytic cleavage of a C(sp3)–C(sp3)-σ-bond rather than the well-known α-C–H-scission. The resulting carbon-centered radicals are used in the ipso-substitution of (hetero)aromatic nitriles proceeding through another single-electron transfer-mediated C–C-bond cleavage and formation.
Single Enantiomer’s Urge to Crystallize in Centrosymmetric Space Groups: Solid Solutions of Phenylpiracetam
2017
A detailed thermochemical and structural study of the phenylpiracetam enantiomer system was performed by characterizing the solid solutions, rationalizing the structural driving force for their formation, as well as identifying a common structural origin responsible for the formation of solid solutions of enantiomers. Enantiomerically pure phenylpiracetam forms two enantiotropically related polymorphs (enant–A and enant–B). The transition point (70(7) °C) was determined based on isobaric heat capacity measurements. Structural studies revealed that enant–A and enant–B crystallize in space groups P1 (Z′ = 4) and P212121 (Z′ = 2), respectively. However, pseudoinversion centers were present res…
Effect of Guest Molecules on Spin Transition Temperature in Loaded Hofmann‐Like Clathrates with Improved Porosity
2020
The synthesis, crystal structure, magnetic and calorimetric studies of a new clathrate compound of the Hofmann-type spin crossover (SCO) metal-organic framework (MOF) {Fe(bpb)[MII(CN)4]}·xGuest (bpb = bis(4-pyridyl)butadiyne, and MII = Ni, Pt) with characteristic fsc topology is reported. The framework {Fe(bpb)[MII(CN)4]} can host up to 1.5 guest molecules of (trifluoromethyl)benzene and display complete one-step cooperative SCO behavior. Our systematic study on {Fe(bpb)[Pt(CN)4]}·xGuest shows a general reciprocal correlation between the SCO temperature with the volume of the guest molecules.