Properties and Reactivity Patterns of AsP3: An Experimental and Computational Study of Group 15 Elemental Molecules
Name
AsP3_final_revised.pdf
Description
Main article
Size
1.18 MB
Format
Adobe PDF
Checksum (MD5)
420b8dd63235f5453a68439d1c47a14c
Author(s)
Cossairt, Brandi M.
Cummins, Christopher C.
Date Issued
October 2009
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Citation
Cossairt, Brandi M., and Christopher C. Cummins. “Properties and Reactivity Patterns of AsP
3
: An Experimental and Computational Study of Group 15 Elemental Molecules.” Journal of the American Chemical Society 131.42 (2009) : 15501-15511.
Version
Author's final manuscript
Abstract
Facile synthetic access to the isolable, thermally robust AsP3 molecule has allowed for a thorough study of its physical properties and reaction chemistry with a variety of transition-metal and organic fragments. The electronic properties of AsP3 in comparison with P4 are revealed by DFT and atoms in molecules (AIM) approaches and are discussed in relation to the observed electrochemical profiles and the phosphorus NMR properties of the two molecules. An investigation of the nucleus independent chemical shifts revealed that AsP3 retains spherical aromaticity. The thermodynamic properties of AsP3 and P4 are described. The reaction types explored in this study include the thermal decomposition of the AsP3 tetrahedron to its elements, the synthesis and structural characterization of [(AsP3)FeCp*(dppe)][BPh4] (dppe = 1,2-bis(diphenylphosphino)ethane), 1, selective single As-P bond cleavage reactions, including the synthesis and structural characterization of AsP3(P(N(iPr)2)N(SiMe3)2)2, 2, and activations of AsP3 by reactive early transition-metal fragments including Nb(H)(η2-tBu(H)C═NAr)(N[CH2tBu]Ar)2 and Mo(N[tBu]Ar)3 (Ar = 3,5-Me2C6H3). In the presence of reducing equivalents, AsP3 was found to allow access to [Na][E3Nb(ODipp)3] (Dipp = 2,6-diisopropylphenyl) complexes (E = As or P) which themselves allow access to mixtures of AsnP4−n (n = 1−4).
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/ja906294m
