Abstract
The crystal structure of the new cation ic Rh1 complex trans-[Rh(CO)2(L)2]BF4 (L = a 2-(diisopropylphosphino)isodurene) was found to exhibit a nonlinear OC-Rh-CO fragment and weak intramolecular C-H⋯Rh interactions. These interactions, which have also been shown to occur in solution, have been examined by density functional theory calculations and found to be inextricably linked to the presence of the distorted OC-Rh-CO fragment. This linkage has also been demonstrated by comparison with a highly similar RhI complex, in which these C-H⋯Rh interactions are absent. Furthermore, the presence of these weak interactions has been shown to have a significant effect on the reactivity of the metal center.
| Original language | English |
|---|---|
| Pages (from-to) | 8183-8194 |
| Number of pages | 12 |
| Journal | Chemistry - A European Journal |
| Volume | 14 |
| Issue number | 27 |
| DOIs | |
| Publication status | Published - Sep 19 2008 |
Fingerprint
Keywords
- Anagostic interaction
- C-H activation
- Carbonyl ligands
- Phosphines
- Rhodium
ASJC Scopus subject areas
- Chemistry(all)
Cite this
The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)2(phosphine)2]+ : An experimental and theoretical examination. / Montag, Michael; Efremenko, Irena; Cohen, Revital; Leitus, Gregory; Shimon, Linda J W; Diskin-Posner, Yael; Ben-David, Yehoshoa; Martin, Jan M L; Milstein, David.
In: Chemistry - A European Journal, Vol. 14, No. 27, 19.09.2008, p. 8183-8194.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - The impact of weak C-H⋯Rh interactions on the structure and reactivity of trans-[Rh(CO)2(phosphine)2]+
T2 - An experimental and theoretical examination
AU - Montag, Michael
AU - Efremenko, Irena
AU - Cohen, Revital
AU - Leitus, Gregory
AU - Shimon, Linda J W
AU - Diskin-Posner, Yael
AU - Ben-David, Yehoshoa
AU - Martin, Jan M L
AU - Milstein, David
PY - 2008/9/19
Y1 - 2008/9/19
N2 - The crystal structure of the new cation ic Rh1 complex trans-[Rh(CO)2(L)2]BF4 (L = a 2-(diisopropylphosphino)isodurene) was found to exhibit a nonlinear OC-Rh-CO fragment and weak intramolecular C-H⋯Rh interactions. These interactions, which have also been shown to occur in solution, have been examined by density functional theory calculations and found to be inextricably linked to the presence of the distorted OC-Rh-CO fragment. This linkage has also been demonstrated by comparison with a highly similar RhI complex, in which these C-H⋯Rh interactions are absent. Furthermore, the presence of these weak interactions has been shown to have a significant effect on the reactivity of the metal center.
AB - The crystal structure of the new cation ic Rh1 complex trans-[Rh(CO)2(L)2]BF4 (L = a 2-(diisopropylphosphino)isodurene) was found to exhibit a nonlinear OC-Rh-CO fragment and weak intramolecular C-H⋯Rh interactions. These interactions, which have also been shown to occur in solution, have been examined by density functional theory calculations and found to be inextricably linked to the presence of the distorted OC-Rh-CO fragment. This linkage has also been demonstrated by comparison with a highly similar RhI complex, in which these C-H⋯Rh interactions are absent. Furthermore, the presence of these weak interactions has been shown to have a significant effect on the reactivity of the metal center.
KW - Anagostic interaction
KW - C-H activation
KW - Carbonyl ligands
KW - Phosphines
KW - Rhodium
UR - http://www.scopus.com/inward/record.url?scp=53849087194&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=53849087194&partnerID=8YFLogxK
U2 - 10.1002/chem.200801171
DO - 10.1002/chem.200801171
M3 - Article
C2 - 18698575
AN - SCOPUS:53849087194
VL - 14
SP - 8183
EP - 8194
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 27
ER -