Iodobismuthate(III) and Iodobismuthate(III)/Iodocuprate(I) Complexes with Organic Ligands. Issue 43 (21st November 2017)

• Record Type: Journal Article
• Authors: Kelly, Andrew W.; Wheaton, Amelia M.; Nicholas, Aaron D.; Barnes, Francis H.; Patterson, Howard H.; Pike, Robert D.
• Is Part Of: European journal of inorganic chemistry. Issue 43(2017)
• Page Start: 4990
• Page End: 5000
• Publication Date: 2017-11-21
• Subjects: Bismuth -- Iodine -- Copper -- Structure elucidation -- Density functional calculations; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201701052
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Pyridine ligand complexes of [Bu4 N][BiI4 ] were prepared using chelating ligands 2, 2′‐bipyridyl (2, 2′‐Bpy), 1, 10‐phenanthroline (Phen), and 4‐nitro‐1, 10‐phenanthroline (NO2 Phen), producing monomeric complexes [Bu4 N][(2, 2′‐Bpy)BiI4 ], [Bu4 N][(Phen)BiI4 ], and [Bu4 N][(NO2 Phen)BiI4 ], and bridging ligands 4, 4′‐bipyridyl (4, 4′‐Bpy), pyrazine (Pyz), and aminopyrazine (NH2 Pyz) resulting in formation of polymers [Bu4 N] n [(4, 4′‐Bpy)BiI4 ] n and [Bu4 N] 2n [(RPyz)Bi2 I8 ] n (R = H, NH2 ). The latter contain edge‐sharing Bi2 I8 dimers. Organic ligand Bi III /Cu I clusters [Bu4 N]2 [L2 Bi2 Cu2 I10 ] {L = PPh3, P(OPh)3 } and [Bu4 N]2 [PyBi2 Cu2 I10 ] (Py = pyridine) have been prepared. All bismuthate(III) centers are distorted octahedra and all cuprate(I) centers are tetrahedral, with organic ligands bonded to Cu I . The first neutral BiI3 /CuI organic ligand complex [BiCu3 I6 (PPh3 )6 ] is reported. Diffuse reflectance spectroscopy measurements reveal strong absorption bands for both iodobismuthate(III) and iodocuprate(I)/bismuthate(III) complexes in the UV and visible range. Despite the similarity in absorption bands, DFT calculations support a distinct shift in transition from a mixed halide/metal‐to‐ligand charge transfer (X/MLCT) to a metal–halide cluster‐centered transition upon incorporation of copper(I) into the cluster. Abstract : Iodobismuthate(III) and iodobismuthate(III)/cuprate(I) complexes with chelating and bridging organic ligands are structurally characterized, including the first iodobismuthate(III) metal–organic polymers. Bi III /Cu I clusters show ligand binding at copper. Diffuse reflectance spectra show UV/Vis absorptions, and DFT calculations suggest MLCT and metal–halide centered transitions.