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Title: Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds
Authors: Shi, Xiaoyan
Martin, Katherine Ann
Liang, Rong Zheng
Star, Daniel G.
Li, Yongxin
Ganguly, Rakesh
Sim, Ying
Tan, Davin
Díaz, Jesús
García, Felipe
Keywords: Science::Chemistry
Issue Date: 2018
Source: Shi, Y. X., Martin, K. A., Liang, R. Z., Star, D. G., Li, Y., Ganguly, R., . . . García, F. (2018). Synthesis of unique phosphazane macrocycles via steric activation of C-N bonds. Inorganic Chemistry, 57(17), 10993-11004. doi:10.1021/acs.inorgchem.8b01596
Journal: Inorganic Chemistry
Abstract: Herein we describe that oxidation reactions of the dimeric cyclophosphazanes, [{P(μ-NR)}2(μ-NR)]2, R = tBu (1), to produce a series of diagonally dioxidized products P4(μ-N tBu)6E2 [E = O (2), S (3), and Se (4)] and tetraoxidized frameworks. The latter display an unexpected C-N bond activation and cleavage to produce a series of novel phosphazane macrocyclic arrangements containing newly formed N-H bonds. Macromolecules P4(μ-N tBu)4(μ-NH)2O4 (5) and P4(μ-N tBu)3(μ-NH)3E4, E = S (6) and Se (7), dicleaved and tricleaved products, respectively, are rare examples of dimeric macrocycles containing NH bridging groups. Our theoretical and experimental studies illustrate that the extent to which these C-N bonds are cleaved can be controlled by modification of steric parameters in their synthesis, by adjusting either the steric bulk of the substituents in the parent framework or the size of the chalcogen element introduced during the oxidation process. Our findings represent new synthetic pathways for the synthesis of otherwise-elusive macrocycle arrangements within the phosphazane family.
ISSN: 0020-1669
DOI: 10.1021/acs.inorgchem.8b01596
Rights: © 2018 American Chemical Society. All rights reserved.
Fulltext Permission: none
Fulltext Availability: No Fulltext
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