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dc.contributor.authorShi, Xiaoyanen_US
dc.contributor.authorMartin, Katherine Annen_US
dc.contributor.authorLiang, Rong Zhengen_US
dc.contributor.authorStar, Daniel G.en_US
dc.contributor.authorLi, Yongxinen_US
dc.contributor.authorGanguly, Rakeshen_US
dc.contributor.authorSim, Yingen_US
dc.contributor.authorTan, Davinen_US
dc.contributor.authorDíaz, Jesúsen_US
dc.contributor.authorGarcía, Felipeen_US
dc.identifier.citationShi, 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.8b01596en_US
dc.description.abstractHerein 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.en_US
dc.description.sponsorshipASTAR (Agency for Sci., Tech. and Research, S’pore)en_US
dc.description.sponsorshipMOE (Min. of Education, S’pore)en_US
dc.relation.ispartofInorganic Chemistryen_US
dc.rights© 2018 American Chemical Society. All rights reserved.en_US
dc.titleSynthesis of unique phosphazane macrocycles via steric activation of C-N bondsen_US
dc.typeJournal Articleen
dc.contributor.schoolSchool of Physical and Mathematical Sciencesen_US
dc.subject.keywordsGroup 16 Compoundsen_US
dc.subject.keywordsBond Cleavageen_US
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