Bridging 1,2-Bis(diphenylphosphino)methane Ligands Facilitate the Formation of Binuclear Complexes with Both Two-Coordinate and Three-Coordinate Gold(I) Ions

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Inorganic Chemistry Pub Date : 2024-12-18 DOI:10.1021/acs.inorgchem.4c03657

Sarah Costa, Sarah M. Chui, Katelyn A. Espinoza, James C. Fettinger, Alan L. Balch

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Abstract

Five new crystalline gold(I) complexes β-Au₂(μ-dppm)₂Br₂·2CH₂Cl₂ (1), [Au₂(μ- dppm)₂Br]Br·2CH₂Cl₂ (2), [Au₂(μ-dppm)₂Br](PF₆) (3), [Au₂(μ-dppm)₂Cl](BPh₄)·3CH₂Cl₂ (4) and [Au₂(μ-dppm)₂]Cl(AsF₆)·2CH₂Cl₂ (5) (where dppm is bis(diphenylphosphino)methane) have been prepared and structurally characterized by single crystal X-ray diffraction. Colorless β-Au₂(μ-dppm)₂Br₂·2CH₂Cl₂ (1) has centrosymmetric structure with two three-coordinate gold(I) ions held in close proximity by the dppm ligands. Crystals of [Au₂(μ- dppm)₂Br]Br·2CH₂Cl₂ (2), [Au₂(μ-dppm)₂Br](PF₆) (3), and [Au₂(μ-dppm)₂Cl](BPh₄)·3CH₂Cl₂ (4) have a cation with an unusual arrangement that binds a two-coordinate gold(I) ion to a three-coordinate gold(I) ion through an aurophilic interaction. Whereas Au₂(μ-dppm)₂Cl(BPh₄)·3CH₂Cl₂ (4) has a chloride ion bound to only one of the gold ions in the complex, [Au₂(μ-dppm)₂]Cl(AsF₆)·2CH₂Cl₂ (5) has an ion paired chloride ion that is symmetrically disposed between the two gold ions at a rather long distance. Each complex displays luminescence under UV irradiation.

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五种新的结晶金（I）配合物 β-Au2(μ-dppm)2Br2-2CH2Cl2 (1)、[Au2(μ- dppm)2Br]Br-2CH2Cl2 (2)、[Au2(μ- dppm)2Br](PF6) (3)、(4) 和 [Au2(μ-dppm)2]Cl(AsF6)-2CH2Cl2 (5)（其中 dppm 为双(二苯基膦)甲烷），并通过单晶 X 射线衍射进行了结构表征。无色的 β-Au2(μ-dppm)2Br2-2CH2Cl2（1）具有中心对称结构，两个三配位金（I）离子被 dppm 配体紧紧包围。[Au2(μ-dppm)2Br]Br-2CH2Cl2(2)、[Au2(μ-dppm)2Br](PF6)(3)和[Au2(μ-dppm)2Cl](BPh4)-3CH2Cl2(4)晶体中的阳离子具有不寻常的排列方式，通过亲欧相互作用将二配位金（I）离子与三配位金（I）离子结合在一起。Au2(μ-dppm)2Cl(BPh4)-3CH2Cl2（4）中的氯离子只与复合物中的一个金离子结合，而[Au2(μ-dppm)2]Cl(AsF6)-2CH2Cl2（5）中的离子配对氯离子以相当长的距离对称地排列在两个金离子之间。在紫外线照射下，每个复合物都会发光。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.