UA cloudflare authentication

 

The Synthesis, Characterization and Dehydrogenation of Sigma-Complexes of BN-Cyclohexanes

Simple item page
dc.contributor.authorKumar, Amit
dc.contributor.authorIshibashi, Jacob S. A.
dc.contributor.authorHooper, Thomas N.
dc.contributor.authorMikulas, Tanya C.
dc.contributor.authorDixon, David A.
dc.contributor.authorLiu, Shih-Yuan
dc.contributor.authorWeller, Andrew S.
dc.contributor.otherUniversity of Oxford
dc.contributor.otherBoston College
dc.contributor.otherUniversity of Alabama Tuscaloosa
dc.date.accessioned2023-09-28T19:19:09Z
dc.date.available2023-09-28T19:19:09Z
dc.date.issued2016
dc.description.abstractThe coordination chemistry of the 1,2-BN-cyclohexanes 2,2-R-2-1,2-B,N-C4H10 (R-2=HH, MeH, Me-2) with Ir and Rh metal fragments has been studied. This led to the solution (NMR spectroscopy) and solid-state (X-ray diffraction) characterization of [Ir(PCy3)(2)(H)(2)(eta(2)eta(2)-H2BNR2C4H8)][BAr4F] (NR2=NH2, NMeH) and [Rh(iPr(2)PCH(2)CH(2)CH(2)PiPr(2))(eta(2)eta(2)-H2BNR2C4H8)][ BAr4F] (NR2=NH2, NMeH, NMe2). For NR2=NH2 subsequent metal-promoted, dehydrocoupling shows the eventual formation of the cyclic tricyclic borazine [BNC4H8](3), via amino-borane and, tentatively characterized using DFT/GIAO chemical shift calculations, cycloborazane intermediates. For NR2=NMeH the final product is the cyclic amino-borane HBNMeC4H8. The mechanism of dehydrogenation of 2,2-H,Me-1,2-B,N-C4H10 using the {Rh(iPr(2)PCH(2)CH(2)CH(2)PiPr(2))}+ catalyst has been probed. Catalytic experiments indicate the rapid formation of a dimeric species, [Rh-2(iPr(2)PCH(2)CH(2)CH(2)PiPr(2))(2)H-5][BAr4F]. Using the initial rate method starting from this dimer, a first-order relationship to [amine-borane], but half-order to [Rh] is established, which is suggested to be due to a rapid dimer-monomer equilibrium operating.en_US
dc.format.mediumelectronic
dc.format.mimetypeapplication/pdf
dc.identifier.citationKumar, A., Ishibashi, J. S. A., Hooper, T. N., Mikulas, T. C., Dixon, D. A., Liu, S., & Weller, A. S. (2015). The Synthesis, Characterization and Dehydrogenation of Sigma‐Complexes of BN‐Cyclohexanes. In Chemistry – A European Journal (Vol. 22, Issue 1, pp. 310–322). Wiley. https://doi.org/10.1002/chem.201502986
dc.identifier.doi10.1002/chem.201502986
dc.identifier.orcidhttps://orcid.org/0000-0003-1646-8081
dc.identifier.orcidhttps://orcid.org/0000-0002-8175-8221
dc.identifier.orcidhttps://orcid.org/0000-0003-3148-9147
dc.identifier.orcidhttps://orcid.org/0000-0001-7768-0938
dc.identifier.orcidhttps://orcid.org/0000-0003-2045-4387
dc.identifier.urihttps://ir.ua.edu/handle/123456789/11292
dc.languageEnglish
dc.language.isoen_US
dc.publisherWiley-VCH
dc.subjectamine-borane
dc.subjectcatalysis
dc.subjectiridium
dc.subjectphosphine
dc.subjectrhodium
dc.subjectFREE HYDROGEN-TRANSFER
dc.subjectAMINE-BORANES
dc.subjectAMMONIA-BORANE
dc.subjectDEHYDROCOUPLING REACTIONS
dc.subjectDIMETHYLAMINE-BORANE
dc.subjectBASIS-SETS
dc.subjectRHODIUM
dc.subjectRUTHENIUM
dc.subjectMECHANISM
dc.subjectBORON
dc.subjectChemistry, Multidisciplinary
dc.titleThe Synthesis, Characterization and Dehydrogenation of Sigma-Complexes of BN-Cyclohexanesen_US
dc.typeArticle
dc.typetext

Files

Original bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
PMC4818983-CHEM-22-310.pdf
Size:
2.65 MB
Format:
Adobe Portable Document Format
Download

Collections

Research and Publications - Department of Chemistry & Biochemistry