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Reaction Chemistry at Discrete Organometallic Fragments on Black Phosphorus
Authors:Kendahl L Walz Mitra  Michael Riehs  Andrei Draguicevic  William A Swann  Christina W Li  Alexandra Velian
Institution:1. Department of Chemistry, University of Washington, Seattle, WA 98195 USA;2. Department of Chemistry, Purdue University, West Lafayette, IN 47907 USA
Abstract:Black phosphorus (bP) is a two-dimensional van der Waals material unique in its potential to serve as a support for single-site catalysts due to its similarity to molecular phosphines, ligands quintessential in homogeneous catalysis. However, there is a scarcity of synthetic methods to install single metal centers on the bP lattice. Here, we demonstrate the functionalization of bP nanosheets with molecular Re and Mo complexes. A suite of characterization techniques, including infrared, X-ray photoelectron and X-ray absorption spectroscopy as well as scanning transmission electron microscopy corroborate that the functionalized nanosheets contain a high density of discrete metal centers directly bound to the bP surface. Moreover, the supported metal centers are chemically accessible and can undergo ligand exchange transformations without detaching from the surface. The steric and electronic properties of bP as a ligand are estimated with respect to molecular phosphines. Sterically, bP resembles tri(tolyl)phosphine when monodentate to a metal center, and bis(diphenylphosphino)propane when bidentate, whereas electronically bP is a σ-donor as strong as a trialkyl phosphine. This work is foundational in elucidating the nature of black phosphorus as a ligand and underscores the viability of using bP as a basis for single-site catalysts.
Keywords:Black Phosphorus  Molecular Surface Modification  Single-Site Catalysts  Single-Site Metal Coordination
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