Dataset Information

Formation of Heterobimetallic Complexes by Addition of d¹⁰-Metal Ions to [(Me₃P)_xM(2-C₆F₄PPh₂)₂] (x = 1, 2; M = Ni and Pt): A Synthetic and Computational Study of Metallophilic Interactions.

ABSTRACT: Treatment of the bis(chelate) complexes trans-[M(κ²-2-C₆F₄PPh₂)₂] (trans-1M; M = Ni, Pt) and cis-[Pt(κ²-2-C₆F₄PPh₂)₂] (cis-1Pt) with equimolar amounts or excess of PMe₃ solution gave complexes of the type [(Me₃P)_xM(2-C₆F₄PPh₂)₂] (x = 2: 2M^a, 2M^b x = 1: 3M^a, 3M^b; M = Ni, Pt). The reactivity of complexes of the type 2M and 3M toward monovalent coinage metal ions (M' = Cu, Ag, Au) was investigated next to the reaction of 1M toward [AuCl(PMe₃)]. Four different complex types [(Me₃P)₂M(μ-2-C₆F₄PPh₂)₂M'Cl] (5MM'; M = Ni, Pt; M' = Cu, Ag, Au), [(Me₃P)M(κ²-2-C₆F₄PPh₂)(μ-2-C₆F₄PPh₂)M'Cl]_x (x = 1: 6MM'; M = Pt; M' = Cu, Au; x = 2: 6PtAg), head-to-tail-[(Me₃P)ClM(μ-2-C₆F₄PPh₂)₂M'] (7MM'; M = Ni, Pt; M' = Au), and head-to-head-[(Me₃P)ClM(μ-2-C₆F₄PPh₂)₂M'] (8MM'; M = Ni, Pt; M' = Cu, Ag, Au) were observed. Single-crystal X-ray analyses of complexes 5-8 revealed short metal-metal separations (2.7124(3)-3.3287(7) Å), suggestive of attractive metal-metal interactions. Quantum chemical calculations (atoms in molecules (AIM), electron localization function (ELF), non-covalent interaction (NCI), and natural bond orbital (NBO)) gave theoretical support that the interaction characteristics reach from a pure attractive non-covalent to an electron-shared (covalent) character.

SUBMITTER: Gericke R

PROVIDER: S-EPMC10265710 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

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Publications

Formation of Heterobimetallic Complexes by Addition of d10-Metal Ions to [(Me3P)xM(2-C6F4PPh2)2] (x = 1, 2; M = Ni and Pt): A Synthetic and Computational Study of Metallophilic Interactions.

Gericke Robert R Bennett Martin A MA Privér Steven H SH Bhargava Suresh K SK

Inorganic chemistry 20230531 23

Treatment of the bis(chelate) complexes trans-[M(κ2-2-C6F4PPh2)2] (trans-1M; M = Ni, Pt) and cis-[Pt(κ2-2-C6F4PPh2)2] (cis-1Pt) with equimolar amounts or excess of PMe3 solution gave complexes of the type [(Me3P)xM(2-C6F4PPh2)2] (x = 2: 2Ma</ ...[more]

PMID: 37254744

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Project description:Transition metal (TM) complexes are widely used in catalysis, photochemical energy conversion, and sensing. Understanding factors that affect ligand loss from TM complexes at interfaces is important both for generating catalytically-active undercoordinated TM complexes and for controlling the degradation pathways of photosensitizers and photoredox catalysts. Herein, we demonstrate that well-defined TM complexes prepared on surfaces using ion soft landing undergo substantial structural rearrangements resulting in ligand loss and formation of both stable and reactive undercoordinated species. We employ nickel bipyridine (Ni-bpy) cations as a model system and explore their structural reorganization on surfaces using a combination of experimental and computational approaches. The controlled preparation of surface layers by mass-selected deposition of [Ni(bpy)3]2+ cations provides insights into the chemical reactivity of these species on surfaces. Both surface characterization using mass spectrometry and electronic structure calculations using density functional theory (DFT) indicate that [Ni(bpy)3]2+ undergoes a substantial geometry distortion on surfaces in comparison with its gas-phase structure. This distortion reduces the ligand binding energy and facilitates the formation of the undercoordinated [Ni(bpy)2]2+. Additionally, charge reduction by the soft landed [Ni(bpy)3]2+ facilitates ligand loss. We observe that ligand loss is inhibited by co-depositing [Ni(bpy)3]2+ with a stable anion such as closo-dodecaborate dianion, [B12F12]2-. The strong electrostatic interaction between [Ni(bpy)3]2+ and [B12F12]2- diminishes the distortion of the cation due to interactions with the surface. This interaction stabilizes the soft landed cation by reducing the extent of charge reduction and its structural reorganization. Overall, this study shows the intricate interplay of charge state, ion surface interactions, and stabilization by counterions on the structure and reactivity of metal complexes on surfaces. The combined experimental and computational approach used in this study offers detailed insights into factors that affect the integrity and stability of active species relevant to energy production and catalysis.

Dataset Information

Formation of Heterobimetallic Complexes by Addition of d¹⁰-Metal Ions to [(Me₃P)_xM(2-C₆F₄PPh₂)₂] (x = 1, 2; M = Ni and Pt): A Synthetic and Computational Study of Metallophilic Interactions.

Publications

Formation of Heterobimetallic Complexes by Addition of d<sup>10</sup>-Metal Ions to [(Me<sub>3</sub>P)<sub><i>x</i></sub>M(2-C<sub>6</sub>F<sub>4</sub>PPh<sub>2</sub>)<sub>2</sub>] (<i>x</i> = 1, 2; M = Ni and Pt): A Synthetic and Computational Study of Metallophilic Interactions.

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