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https://hdl.handle.net/10356/142688
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. | URI: | https://hdl.handle.net/10356/142688 | ISSN: | 0020-1669 | DOI: | 10.1021/acs.inorgchem.7b02579 | Schools: | School of Physical and Mathematical Sciences | Rights: | © 2017 American Chemical Society. All rights reserved. | Fulltext Permission: | none | Fulltext Availability: | No Fulltext |
Appears in Collections: | SPMS Journal Articles |
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