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Title: E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations
Authors: Đorđević, Nemanja
Ganguly, Rakesh
Petković, Milena
Vidović, Dragoslav
Keywords: Science::Chemistry
Issue Date: 2017
Source: Đorđević, N., Ganguly, R., Petković, M., & Vidović, D. (2017). E-H (E = B, Si, C) Bond activation by tuning structural and electronic properties of phosphenium cations. Inorganic chemistry, 56(23), 14671–14681. doi:10.1021/acs.inorgchem.7b02579
Journal: Inorganic chemistry
Abstract: In this work, strategic enhancement of electrophilicity of phosphenium cations for the purpose of small-molecule activation was described. Our synthetic methodology for generation of novel two-coordinate phosphorus(III)-based compounds [{C6H4(MeN)2C}2C·PR]2+ ([2a]2+, R = NiPr2; [2b]2+, R = Ph) was based on the exceptional electron-donating properties of the carbodicarbene ligand (CDC). The effects of P-centered substituent exchange and increase in the overall positive charge on small substrate activation were comparatively determined by incorporating the bis(amino)phosphenium ion [(iPr2N)2P]+ ([1]+) in this study. Implemented structural and electronic modifications of phosphenium salts were computationally verified and subsequently confirmed by isolation and characterization of the corresponding E-H (E = B, Si, C) bond activation products. While both phosphenium mono- and dications oxidatively inserted/cleaved the B-H bond of Lewis base stabilized boranes, the increased electrophilicity of doubly charged species also afforded the activation of significantly less hydridic Si-H and C-H bonds. The preference of [2a]2+ and [2b]2+ to abstract the hydride rather than to insert into the corresponding bond of silanes, as well as the formation of the carbodicarbene-stabilized parent phosphenium ion [{C6H4(MeN)2C}2C·PH2]+ ([2·PH2]+) were experimentally validated.
ISSN: 0020-1669
DOI: 10.1021/acs.inorgchem.7b02579
Rights: © 2017 American Chemical Society. All rights reserved.
Fulltext Permission: none
Fulltext Availability: No Fulltext
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