Abstract
The homolytic bond dissociation energies of a series of five- and six-coordinate mono- and dihydride complexes of the type HM(diphosphine)2 and [H2M(diphosphine)2]+ (where M = Co, Rh, and Ir) are calculated and compared with experimental values. This work probes the relationship between the homolytic bond dissociation energies (HMBDEs) of these complexes in these two different coordination environments and formal oxidation states. The results of these calculations and previous experimental observations suggest that for M = Rh the HMBDE of the five-coordinate HM(diphosphine)2 species are 0-2 kcal/mol larger than the HMBDE of the corresponding six-coordinate [H2M(diphosphine)2]+ species. For M = Ir the bond energies of the five- and six-coordinate complexes are nearly the same and for M = Co the six-coordinate species are 1-5 kcal/mol less than the corresponding five-coordinate species. Simplified models of large and complicated ligands seem to capture the essential trends and give very good estimates of these thermodynamic properties compared with experimentally available data that are difficult to obtain. (Chemical Equation Presented).
| Original language | English |
|---|---|
| Pages (from-to) | 1993-2000 |
| Number of pages | 8 |
| Journal | Journal of Physical Chemistry A |
| Volume | 121 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - Mar 9 2017 |
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- Physical and Theoretical Chemistry
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Trends in Homolytic Bond Dissociation Energies of Five- and Six-Coordinate Hydrides of Group 9 Transition Metals : Co, Rh, Ir. / Glezakou, Vassiliki Alexandra; Rousseau, Roger; Elbert, Stephen T.; Franz, James A.
In: Journal of Physical Chemistry A, Vol. 121, No. 9, 09.03.2017, p. 1993-2000.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Trends in Homolytic Bond Dissociation Energies of Five- and Six-Coordinate Hydrides of Group 9 Transition Metals
T2 - Co, Rh, Ir
AU - Glezakou, Vassiliki Alexandra
AU - Rousseau, Roger
AU - Elbert, Stephen T.
AU - Franz, James A.
PY - 2017/3/9
Y1 - 2017/3/9
N2 - The homolytic bond dissociation energies of a series of five- and six-coordinate mono- and dihydride complexes of the type HM(diphosphine)2 and [H2M(diphosphine)2]+ (where M = Co, Rh, and Ir) are calculated and compared with experimental values. This work probes the relationship between the homolytic bond dissociation energies (HMBDEs) of these complexes in these two different coordination environments and formal oxidation states. The results of these calculations and previous experimental observations suggest that for M = Rh the HMBDE of the five-coordinate HM(diphosphine)2 species are 0-2 kcal/mol larger than the HMBDE of the corresponding six-coordinate [H2M(diphosphine)2]+ species. For M = Ir the bond energies of the five- and six-coordinate complexes are nearly the same and for M = Co the six-coordinate species are 1-5 kcal/mol less than the corresponding five-coordinate species. Simplified models of large and complicated ligands seem to capture the essential trends and give very good estimates of these thermodynamic properties compared with experimentally available data that are difficult to obtain. (Chemical Equation Presented).
AB - The homolytic bond dissociation energies of a series of five- and six-coordinate mono- and dihydride complexes of the type HM(diphosphine)2 and [H2M(diphosphine)2]+ (where M = Co, Rh, and Ir) are calculated and compared with experimental values. This work probes the relationship between the homolytic bond dissociation energies (HMBDEs) of these complexes in these two different coordination environments and formal oxidation states. The results of these calculations and previous experimental observations suggest that for M = Rh the HMBDE of the five-coordinate HM(diphosphine)2 species are 0-2 kcal/mol larger than the HMBDE of the corresponding six-coordinate [H2M(diphosphine)2]+ species. For M = Ir the bond energies of the five- and six-coordinate complexes are nearly the same and for M = Co the six-coordinate species are 1-5 kcal/mol less than the corresponding five-coordinate species. Simplified models of large and complicated ligands seem to capture the essential trends and give very good estimates of these thermodynamic properties compared with experimentally available data that are difficult to obtain. (Chemical Equation Presented).
UR - http://www.scopus.com/inward/record.url?scp=85015615455&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85015615455&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.6b11655
DO - 10.1021/acs.jpca.6b11655
M3 - Article
AN - SCOPUS:85015615455
VL - 121
SP - 1993
EP - 2000
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 9
ER -