Abstract
Reaction of Cp*Os(CO)2Cl with [Et3Si][BAr 4F] under hydrogen gas affords the cationic hydrogen complex [Cp*Os(CO)2(H2)][BAr4 F] (1) (Cp* = C5Me5; ArF = C6F5). When this reaction is carried out with HD gas, complex 1-d1 results, with JHD -24.5 Hz. When solutions of complex 1 are monitored by 1H NMR spectroscopy over several days, the gradual formation of a trans dihydride species is observed. Similarly, reaction of CpOs(dppm)Br with Na[BArF*4] (Ar F* = 3,5-(CF3)2C6H 3) under hydrogen affords the cationic dihydride complex [CpOs(dppm)H2][BArF*4] (2). At 295 K, complex 2 exists as a 10:1 mixture of cis and trans isomers. The 1H NMR spectrum of the cis form in the hydride region exhibits a triplet with JHP = 6.5 Hz, due to rapid exchange of the hydrogen atoms. At low temperature, static spectra of the HH′PP′ spin system can be obtained, revealing quantum mechanical exchange coupling between the two hydride ligands. The observed JHH′ is temperature dependent, varying from 133 Hz at 141 K to 176 Hz at 198 K. This is the first report of detectable exchange coupling between pairs of chemically equivalent hydrogen atoms.
| Original language | English |
|---|---|
| Pages (from-to) | 2291-2295 |
| Number of pages | 5 |
| Journal | Organometallics |
| Volume | 26 |
| Issue number | 9 |
| DOIs | |
| Publication status | Published - Apr 23 2007 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
Cationic dihydrogen/dihydride complexes of osmium : Structure and dynamics. / Egbert, Jonathan D.; Bullock, R Morris; Heinekey, D. Michael.
In: Organometallics, Vol. 26, No. 9, 23.04.2007, p. 2291-2295.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Cationic dihydrogen/dihydride complexes of osmium
T2 - Structure and dynamics
AU - Egbert, Jonathan D.
AU - Bullock, R Morris
AU - Heinekey, D. Michael
PY - 2007/4/23
Y1 - 2007/4/23
N2 - Reaction of Cp*Os(CO)2Cl with [Et3Si][BAr 4F] under hydrogen gas affords the cationic hydrogen complex [Cp*Os(CO)2(H2)][BAr4 F] (1) (Cp* = C5Me5; ArF = C6F5). When this reaction is carried out with HD gas, complex 1-d1 results, with JHD -24.5 Hz. When solutions of complex 1 are monitored by 1H NMR spectroscopy over several days, the gradual formation of a trans dihydride species is observed. Similarly, reaction of CpOs(dppm)Br with Na[BArF*4] (Ar F* = 3,5-(CF3)2C6H 3) under hydrogen affords the cationic dihydride complex [CpOs(dppm)H2][BArF*4] (2). At 295 K, complex 2 exists as a 10:1 mixture of cis and trans isomers. The 1H NMR spectrum of the cis form in the hydride region exhibits a triplet with JHP = 6.5 Hz, due to rapid exchange of the hydrogen atoms. At low temperature, static spectra of the HH′PP′ spin system can be obtained, revealing quantum mechanical exchange coupling between the two hydride ligands. The observed JHH′ is temperature dependent, varying from 133 Hz at 141 K to 176 Hz at 198 K. This is the first report of detectable exchange coupling between pairs of chemically equivalent hydrogen atoms.
AB - Reaction of Cp*Os(CO)2Cl with [Et3Si][BAr 4F] under hydrogen gas affords the cationic hydrogen complex [Cp*Os(CO)2(H2)][BAr4 F] (1) (Cp* = C5Me5; ArF = C6F5). When this reaction is carried out with HD gas, complex 1-d1 results, with JHD -24.5 Hz. When solutions of complex 1 are monitored by 1H NMR spectroscopy over several days, the gradual formation of a trans dihydride species is observed. Similarly, reaction of CpOs(dppm)Br with Na[BArF*4] (Ar F* = 3,5-(CF3)2C6H 3) under hydrogen affords the cationic dihydride complex [CpOs(dppm)H2][BArF*4] (2). At 295 K, complex 2 exists as a 10:1 mixture of cis and trans isomers. The 1H NMR spectrum of the cis form in the hydride region exhibits a triplet with JHP = 6.5 Hz, due to rapid exchange of the hydrogen atoms. At low temperature, static spectra of the HH′PP′ spin system can be obtained, revealing quantum mechanical exchange coupling between the two hydride ligands. The observed JHH′ is temperature dependent, varying from 133 Hz at 141 K to 176 Hz at 198 K. This is the first report of detectable exchange coupling between pairs of chemically equivalent hydrogen atoms.
UR - http://www.scopus.com/inward/record.url?scp=34248371261&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=34248371261&partnerID=8YFLogxK
U2 - 10.1021/om0700718
DO - 10.1021/om0700718
M3 - Article
AN - SCOPUS:34248371261
VL - 26
SP - 2291
EP - 2295
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 9
ER -