Abstract

The experimental Raman spectra of three phosphorus-substituted phosphine boranes with bulky hydrocarbon substituents are presented and compared to the results of electronic structure computations by using the M06-2X method and the 6-311G(2df,-2pd) basis set. Total-energy distributions (TEDs) are calculated to describe the degree of mixing of the dative-bond stretching vibration with other simple internal coordinates. This level of theory is found to accurately reproduce the B-P stretching frequency in all three crystalline solids. The Raman spectra of five smaller B-P-containing molecules, including BH3PH3, are also simulated at this level of theory and compared to previous experimental results. Size does matter: The B-P stretching frequencies of phosphine boranes with bulky hydrocarbon substituents are accurately reproduced by calculations at the M06-2X/6-311G(2df,-2pd) level of theory. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Department(s)

Chemistry

Publication Status

Full Access

Comments

National Science Foundation, Grant CHE-0955550

Keywords and Phrases

dative bonds; density functional calculations; dihydrogen bonding; raman spectroscopy; total-energy distribution

International Standard Serial Number (ISSN)

1439-7641; 1439-4235

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2024 Wiley, All rights reserved.

Publication Date

23 Jun 2014

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