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Reappraising Schmidpeter's bis(iminophosphoranyl)phosphides: coordination to transition metals and bonding analysis.

ABSTRACT: 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) the P-P bonds are normal covalent (i.e. not dative) in both BIPP and TP.

SUBMITTER: Normand AT

PROVIDER: S-EPMC8178813 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Coordination chemistry of disilylated stannylenes with group 10 d10 transition metals: silastannene vs stannylene complexation.

Project description:The coordination behavior of disilylated stannylenes toward zerovalent group 10 transition metal complexes was studied. This was accomplished by reactions of PEt3 adducts of disilylated stannylenes with zerovalent group 10 transition metal complexes. The thus obtained products differed between the first row example nickel and its heavier congeners. While with nickel stannylene complex formation was observed, coordination of the stannylenes to palladium and platinum compounds led to unusual silastannene complexes of these metals. A computational model study indicated that in each case metal stannylene complexes were formed first and that the disilylstannylene/silastannene rearrangement occurs only after complexation to the group 10 metal. The isomerization is a two-step process with relatively small barriers, suggesting a thermodynamic control of product formation. In addition, the results of the computational investigation revealed a subtle balance of steric and electronic effects, which determines the relative stability of the metalastannylene complex relative to its silastannene isomer. In the case of cyclic disilylstannylenes, the Pd(0) and Pt(0) silastannene complexes are found to be more stable, while with acyclic disilylstannylenes the Ni(0) stannylene complex is formed preferentially.

| S-EPMC3670429 | biostudies-literature

<i>Quo vadis niobium</i>? Divergent coordination behavior of early-transition metals towards MOF-5.

Project description:Treatment of MOF-5 with NbCl4(THF)2 in acetonitrile leads to incorporation of Nb(iv) centers in a fashion that diverges from the established cation metathesis reactivity of this iconic material. A combination of X-ray absorption spectroscopy analysis and reactivity studies altogether supported by density functional theory computational studies document an unprecedented binding mode for the Zn4O(O2C-)6 secondary building units (SBUs), which in Nb(iv)-MOF-5 function as κ 2-chelating ligands for NbCl4 moieties, with no exchange of Zn2+ observed. This unusual reactivity expands the portfolio of post-synthetic modification techniques available for MOFs, exemplified here by MOF-5, and underscores the diverse coordination environments offered by this and potentially other MOFs towards heterometal species.

| S-EPMC6566296 | biostudies-literature

Topochemical Synthesis of Two-Dimensional Transition-Metal Phosphides Using Phosphorene Templates.

Project description:Transition-metal phosphides (TMPs) have emerged as a fascinating class of narrow-gap semiconductors and electrocatalysts. However, they are intrinsic nonlayered materials that cannot be delaminated into two-dimensional (2D) sheets. Here, we demonstrate a general bottom-up topochemical strategy to synthesize a series of 2D TMPs (e.g. Co2 P, Ni12 P5 , and Cox Fe2-x P) by using phosphorene sheets as the phosphorus precursors and 2D templates. Notably, 2D Co2 P is a p-type semiconductor, with a hole mobility of 20.8?cm2 ?V-1 ?s-1 at 300?K in field-effect transistors. It also behaves as a promising electrocatalyst for the oxygen evolution reaction (OER), thanks to the charge-transport modulation and improved surface exposure. In particular, iron-doped Co2 P (i.e. Co1.5 Fe0.5 P) delivers a low overpotential of only 278?mV at a current density of 10?mA?cm-2 that outperforms the commercial Ir/C benchmark (304?mV).

| S-EPMC6972539 | biostudies-literature

Project description:U(C7H7)2- is a fascinating 5f1 complex whose metal-ligand bonding was assigned in the literature as being very similar to 3d7 cobaltocene, based on a crystal-field theoretical interpretation of the experimental magnetic resonance data. The present work provides an in-depth theoretical study of the electronic structure, bonding, and magnetic properties of the 5f1 U(C7H7)2-vs. 3d metallocenes with V, Co, and Ni, performed with relativistic wavefunction and density functional methods. The ligand to metal donation bonding in U(C7H7)2- is strong and in fact similar to that in vanadocene, in the sense that the highest occupied arene orbitals donate electron density into empty metal orbitals of the same symmetry with respect to the rotational axis (3dπ for V, 5fδ for U), but selectively with α spin (↑). For Co and Ni, the dative bonding from the ligands is β spin (↓) selective into partially filled 3dπ orbitals. In all systems, this spin delocalization triggers spin polarization in the arene σ bonding framework, causing proton spin densities opposite to those of the carbons. As a consequence, the proton spin densities and hyperfine coupling constants are negative for the Co and Ni complex, but positive for vanadocene. The of U(C7H7)2- is negative and similar to that of cobaltocene, but only because of the strong spin-orbit coupling in the actinocene, which causes to be opposite to the sign of the proton spin density. The study contributes to a better understanding of actinide 5f vs. transition metal 3d covalency, and highlights potential pitfalls when interpreting experimental magnetic resonance data in terms of covalent bonding for actinide complexes.

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Bis(dicarbollide) Complexes of Transition Metals as a Platform for Molecular Switches. Study of Complexation of 8,8'-Bis(methylsulfanyl) Derivatives of Cobalt and Iron Bis(dicarbollides).

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| S-EPMC7730339 | biostudies-literature

Bonding Analysis of Compounds with Unusual Coordination of Carbon: Proposed Symmetric Systems with Six-Coordinate Carbon.

Project description:The possibility of carbon tetravalence in geometries other than tetrahedral and of carbon hypervalence has been taken seriously since the 1970s. Computational modeling and subsequent experimental validation have established the existence of molecules with carbon atoms with planar tetravalence and as many as six objects in carbon's coordination sphere. In this work, we develop insight into the nature of bonding to carbon in these unusual environs as provided by Bader's Atoms in Molecules (AIM) analysis of the electron density, along with the electron localization function (ELF) and the non-covalent index (NCI). We review several well-established systems (spiropentadiene dication, hexamethyl benzene dication, dimethanospiro[2.2]octaplane dication, and 1,8-dimethoxy-9-dimethoxyanthracene cation) and propose new D2d-symmetric variants of a hexacoordinated species.

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Transcriptome in yeast by exposure of 7 transition metals

Project description:7 transition metals (silver, arsenic, cadmium, chromium, copper, mercury and zinc) were treated (2hr) on diploid yeast BY4743. Keywords: Response to metals

2008-11-01 | GSE9466 | GEO

Transcriptome of Mycobacterium abscessus in response to transition metals

Project description:Antimicrobial resistance (AMR) is one of the major challenges that humans are facing this century. Understanding the mechanisms behind the rise of AMR is crucial to tackle this global threat. Among the triggers of phenotypic antimicrobial resistance, the contribution of transition metals has been understudied in Mycobacterium abscessus (Mabs), a fast-growing non-tuberculous mycobacterium known for its extreme AMR levels. Deeper understanding of the effects of transition metal ions will be beneficial for our knowledge in AMR and the discovery of potential therapeutic targets. Here, we investigated the impact of transition metal ions, nickel, cobalt and copper on the physiology and drug susceptibility of Mabs.

2024-09-13 | GSE243031 | GEO

Binding of transition metals to S100 proteins.

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| S-EPMC5123432 | biostudies-literature

High-Density Patterned Array Bonding through Void-Free Divinyl Siloxane Bis-Benzocyclobutene Bonding Process.

Project description:Divinylsiloxane-bis-benzocyclobutene (DVS-BCB) has attracted significant attention as an intermediate bonding material, owing to its excellent properties. However, its applications are limited, due to damage to peripheral devices at high curing temperatures and unoptimized compressive pressure. Therefore, it is necessary to explore the compressive pressure condition for DVS-BCB bonding. This study demonstrates an optimization process for void-free DVS-BCB bonding. The process for obtaining void-free DVS-BCB bonding is a vacuum condition of 0.03 Torr, compressive pressure of 0.6 N/mm2, and curing temperature of 250 °C for 1 h. Herein, we define two factors affecting the DVS-BCB bonding quality through the DVS-BCB bonding mechanism. For strong DVS-BCB bonding, void-free and high-density chemical bonds are required. Therefore, we observed the DVS-BCB bonding under various compressive pressure conditions at a relatively low temperature (250 °C). The presence of voids and high-density crosslinking density was examined through near-infrared confocal laser microscopy and Fourier-transform infrared microscopy. We also evaluated the adhesion of the DVS-BCB bonding, using a universal testing machine. The results suggest that the good adhesion with no voids and high crosslinking density was obtained at the compressive pressure condition of 0.6 N/mm2. We believe that the proposed process will be of great significance for applications in semiconductor and device packaging technologies.

| S-EPMC8588381 | biostudies-literature

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