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Bridging 1,2-Bis(diphenylphosphino)methane Ligands Facilitate the Formation of Binuclear Complexes with Both Two-Coordinate and Three-Coordinate Gold(I) Ions
Inorganic Chemistry ( IF 4.3 ) 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

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.

中文翻译:


桥接 1,2-双(二苯基膦基)甲烷配体有助于形成具有二配位和三配位金 (I) 离子的双核配合物



五种新的结晶金(I)络合物 β-Au2(μ-dppm)2Br2·2CH2Cl21), [Au2(μ-dppm)2Br]Br·2CH2Cl22), [Au2(μ-dppm)2Br](PF6) (3), [Au2(μ-dppm)2Cl](BPh4)·3CH2Cl24) 和 [Au2(μ-dppm)2]Cl(AsF6)·2CH2已经制备了 Cl25)(其中 dppm 是双(二苯基膦基)甲烷)并通过单晶 X 射线衍射进行结构表征。无色 β-Au2(μ-dppm)2Br2·2CH2Cl21) 具有中心对称结构,两个三配位金 (I) 离子被 dppm 配体紧紧保持。[Au2(μ-dppm)2Br]Br·2CH2Cl22)、[Au2(μ-dppm)2Br](PF6) (3) 和 [Au2(μ-dppm)2Cl](BPh4)·3CH2Cl24) 的晶体具有一种不寻常排列的阳离子,通过亲uro-abo-interaction将两个配位金(I)离子与一个三个配位金(I)离子结合。Au2(μ-dppm)2Cl(BPh4)·3CH2Cl24) 的氯离子仅与络合物中的金离子之一结合,而 [Au2(μ-dppm)2]Cl(AsF6)·2CH2Cl25) 具有离子对氯离子,该离子以相当长的距离对称分布在两个金离子之间。每种复合物在紫外线照射下都会发光。
更新日期:2024-12-18
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