Anionic Bismuth Oxido Clusters with Pendant Silver Cations: Synthesis and Structures of {[Bi-4(mu(3)-O)(2)(TFA)(9)Ag(tol)(2)](2)} and {Bi-4(mu(3)-O)(2)(TFA)(10)(AgPPh3)(2)}(n)

作者：Andleeb Sohaila; Donaldson Samantha L; Schipper Desmond E; Fernandez Ismael I Loera; Din Imtiaz Ud; Whitmire Kenton H^*

来源：European Journal of Inorganic Chemistry, 2017, 2017(11): 1457-1463.

DOI：10.1002/ejic.201601430

• Bismuth
• Silver
• Arene ligands
• Heterometallic complexes
• Cluster compounds
• Oxido ligands

BiPh3 and trifluoroacetic acid (TFAH) react in toluene in the presence of Ag2O to form {[Bi-4(mu(3)-O)(2)(TFA)(9)Ag(tol)(2)](2)} (1; tol = PhMe). Similarly, BiPh3, TFAH, PPh3, and Ag2O react in hexane to form [Bi-4(mu(3)-O)(2)(TFA)(10)(AgPPh3)(2)] n (2). Both contain {Bi-4(mu(3)-O)(2)} units, which have been previously observed with a variety of carboxylate ligands in neutral compounds and anionic compounds. In contrast to other anionic [Bi-4(mu(3)-O)(2)(TFA)N](N-8)-with metal-based countercations, the Ag+ ions in 1 and 2 are directly attached to oxygen atoms of the TFA-ligands bonded to the bismuth core. A crystallographic evolution was observed for 1. Solvent-rich orthorhombic crystals grew initially on standing. However, by three weeks all crystals had converted to a triclinic unit cell that contained no free solvent. The molecular volume decreased from 3146.11 angstrom(3) (orthorhombic) to 2954.06 angstrom(3) (triclinic). The latter had an intermolecular p-p stacking system between silver-and bismuth-bound toluene molecules, which explains the reorganization to a nonsolvated morphology. Compound 2 crystallizes in the triclinic space group P (1) over bar as a coordination polymer through bridging carboxylate ligands. The presence of the PPh3 ligands on Ag+ results in a higher Ag/Bi ratio than in 1. The importance of Ag2O in generating the oxido ligands was confirmed by the isolation of {[Bi-2(TFA)(6)(TFAH)(tol)](2)}(n) (3) from the reaction of BiPh3 with TFAH in toluene in the absence of the metal oxide.

• 出版日期2017-3-17