Chemical reactivity of the frustrated Lewis pairs in borophosphines : a theoretical analysis of their Lewis acidity, Lewis basicity and Fukui function
The chemical reactivity of a set of borophosphines of the general formula R2B-G-PY2, where G is the connector group between the Lewis acidic site, a borane group, and the Lewis basic site, a phosphine fragment, is theoretically investigated through their Lewis acidity and Lewis basicity, as well as the location of the Fukui function and the shape of the molecular electrostatic potential. The role of some global reactivity descriptors, like the vertical ionization potential, I, and the vertical electron affinity, A, is also analyzed in order to gain a deeper insight on the intrinsic chemical reactivity of these borophosphines. We also use the energies involved in the formation of the adducts between the borophosphine and the ions H- and H+ to estimate the Lewis acidity and Lewis basicity, respectively; by their nature, these energies represent local reactivity descriptors. Some of these borophosphines are able to activate the covalent bond in the hydrogen molecule. Possible paths for the hydrogen release reaction from the zwitterion R[Formula: see text]HB-G-PH[Formula: see text] are studied using the mentioned quantities, suggesting that an intramolecular hydride shift mechanism seems to be more favorable than a proton migration process. The acceptor Fukui function f+(r) proved to be useful to identify the acidic molecular sites for the interaction with the hydride ion and the relative stability of the corresponding adducts is related to the relative values of this function.
Medienart: |
E-Artikel |
---|
Erscheinungsjahr: |
2018 |
---|---|
Erschienen: |
2018 |
Enthalten in: |
Zur Gesamtaufnahme - volume:24 |
---|---|
Enthalten in: |
Journal of molecular modeling - 24(2018), 9 vom: 17. Aug., Seite 238 |
Sprache: |
Englisch |
---|
Beteiligte Personen: |
Méndez, Mariano [VerfasserIn] |
---|
Links: |
---|
Themen: |
Borophosphines |
---|
Anmerkungen: |
Date Completed 20.08.2018 Date Revised 14.11.2018 published: Electronic Citation Status PubMed-not-MEDLINE |
---|
doi: |
10.1007/s00894-018-3776-7 |
---|
funding: |
|
---|---|
Förderinstitution / Projekttitel: |
|
PPN (Katalog-ID): |
NLM287592529 |
---|
LEADER | 01000naa a22002652 4500 | ||
---|---|---|---|
001 | NLM287592529 | ||
003 | DE-627 | ||
005 | 20231225054347.0 | ||
007 | cr uuu---uuuuu | ||
008 | 231225s2018 xx |||||o 00| ||eng c | ||
024 | 7 | |a 10.1007/s00894-018-3776-7 |2 doi | |
028 | 5 | 2 | |a pubmed24n0958.xml |
035 | |a (DE-627)NLM287592529 | ||
035 | |a (NLM)30120567 | ||
040 | |a DE-627 |b ger |c DE-627 |e rakwb | ||
041 | |a eng | ||
100 | 1 | |a Méndez, Mariano |e verfasserin |4 aut | |
245 | 1 | 0 | |a Chemical reactivity of the frustrated Lewis pairs in borophosphines |b a theoretical analysis of their Lewis acidity, Lewis basicity and Fukui function |
264 | 1 | |c 2018 | |
336 | |a Text |b txt |2 rdacontent | ||
337 | |a ƒaComputermedien |b c |2 rdamedia | ||
338 | |a ƒa Online-Ressource |b cr |2 rdacarrier | ||
500 | |a Date Completed 20.08.2018 | ||
500 | |a Date Revised 14.11.2018 | ||
500 | |a published: Electronic | ||
500 | |a Citation Status PubMed-not-MEDLINE | ||
520 | |a The chemical reactivity of a set of borophosphines of the general formula R2B-G-PY2, where G is the connector group between the Lewis acidic site, a borane group, and the Lewis basic site, a phosphine fragment, is theoretically investigated through their Lewis acidity and Lewis basicity, as well as the location of the Fukui function and the shape of the molecular electrostatic potential. The role of some global reactivity descriptors, like the vertical ionization potential, I, and the vertical electron affinity, A, is also analyzed in order to gain a deeper insight on the intrinsic chemical reactivity of these borophosphines. We also use the energies involved in the formation of the adducts between the borophosphine and the ions H- and H+ to estimate the Lewis acidity and Lewis basicity, respectively; by their nature, these energies represent local reactivity descriptors. Some of these borophosphines are able to activate the covalent bond in the hydrogen molecule. Possible paths for the hydrogen release reaction from the zwitterion R[Formula: see text]HB-G-PH[Formula: see text] are studied using the mentioned quantities, suggesting that an intramolecular hydride shift mechanism seems to be more favorable than a proton migration process. The acceptor Fukui function f+(r) proved to be useful to identify the acidic molecular sites for the interaction with the hydride ion and the relative stability of the corresponding adducts is related to the relative values of this function | ||
650 | 4 | |a Journal Article | |
650 | 4 | |a Borophosphines | |
650 | 4 | |a Chemical reactivity | |
650 | 4 | |a Computational and theoretical chemistry | |
650 | 4 | |a Frustrated Lewis pairs | |
650 | 4 | |a Fukui function | |
650 | 4 | |a Lewis acidity | |
650 | 4 | |a Lewis basicity | |
700 | 1 | |a Cedillo, Andrés |e verfasserin |4 aut | |
773 | 0 | 8 | |i Enthalten in |t Journal of molecular modeling |d 1998 |g 24(2018), 9 vom: 17. Aug., Seite 238 |w (DE-627)NLM09744605X |x 0948-5023 |7 nnns |
773 | 1 | 8 | |g volume:24 |g year:2018 |g number:9 |g day:17 |g month:08 |g pages:238 |
856 | 4 | 0 | |u http://dx.doi.org/10.1007/s00894-018-3776-7 |3 Volltext |
912 | |a GBV_USEFLAG_A | ||
912 | |a GBV_NLM | ||
951 | |a AR | ||
952 | |d 24 |j 2018 |e 9 |b 17 |c 08 |h 238 |