Functionalization of Carbon Dioxide with Ethylene at Molybdenum Hydride Complexes

2013 ◽  
Vol 32 (14) ◽  
pp. 3969-3979 ◽  
Author(s):  
Yuanyuan Zhang ◽  
Brian S. Hanna ◽  
Andrew Dineen ◽  
Paul G. Williard ◽  
Wesley H. Bernskoetter
Keyword(s):  
Carbon Dioxide ◽  
Hydride Complexes

Mechanistic Study and Ligand Design for the Formation of Zinc Formate Complexes from Zinc Hydride Complexes and Carbon Dioxide

2014 ◽  
Vol 34 (1) ◽  
pp. 121-126 ◽  
Author(s):  
Chunhua Dong ◽  
Xinzheng Yang ◽  
Jiannian Yao ◽  
Hui Chen
Keyword(s):  
Carbon Dioxide ◽  
Ligand Design ◽  
Mechanistic Study ◽  
Hydride Complexes

scholarly journals Scandium Alkyl and Hydride Complexes Supported by a Pentadentate Diborate Ligand: Reactions with CO2 and N2O

2018 ◽  
Author(s):  
Warren Piers ◽  
Daniel W. Beh ◽  
Iker del Rosal ◽  
Maron Laurent ◽  
Benjamin S. Gelfand ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Slow Rate ◽  
Function Theory ◽  
Density Function Theory ◽  
Insertion Reactions ◽  
Hydride Complexes ◽  
Alkyl Derivatives ◽  
Organolithium Reagents ◽  
Rate Of Reaction ◽  
Sigma Bond

Alkyl and hydrido scandium complexes of the dianionic pentatdentate ligand B<sub>2</sub>Pz<sub>4</sub>Py are reported. The key starting material (B<sub>2</sub>Pz<sub>4</sub>Py)ScCl is readily prepared and alkylated with organolithium reagents RLi (R = CH<sub>3</sub>, CH<sub>2</sub>SiMe<sub>3</sub>, CH<sub>2</sub>SiMe<sub>2</sub>Ph, CH<sub>2</sub>CH<sub>2</sub>CH<sub>3</sub> and CH<sub>2</sub>CHMe<sub>2</sub>) to form alkyl derivatives in 61-93% yields. These compounds are very thermally stable and do not undergo sigma bond metathesis reactions with dihydrogen. The hydrido complex was prepared from (B<sub>2</sub>Pz<sub>4</sub>Py)ScCl and NaHBEt<sub>3</sub> in 80% yield and was found to be more stable by 28 kcal mol<sup>-1</sup> as a dimer, rather than a monomeric hydrido complex. However, the monomer is accessible through dissociation of the dimer at 80˚C. All of the compounds (B<sub>2</sub>Pz<sub>4</sub>Py)ScR react with water to form the bridging oxo dimer (B<sub>2</sub>Pz<sub>4</sub>Py)ScOSc(B<sub>2</sub>Pz<sub>4</sub>Py). The reactivity of the hydrido and methyl complexes towards carbon dioxide was explored; heating to 80˚C results in the formation of k<sup>2</sup> formato and acetate complexes, respectively. The mechanisms were studied via density function theory and distinct transition states for insertion of CO<sub>2</sub> into the Sc-R (R = H, CH<sub>3</sub>) were found, with the insertion into the Sc-CH<sub>3</sub> being more enthalpically difficult (by 18 kcal mol<sup>-1</sup>) than insertion into Sc-H. The slow rate of reaction between [(B<sub>2</sub>Pz<sub>4</sub>Py)ScH]<sub>2</sub> and CO<sub>2</sub> is attributed to the barrier associated with dimer dissociation. In both insertion reactions, the kinetic products are k<sup>1</sup> formato or acetate complexes that are only slightly less stable than the observed k<sup>2</sup> derivatives. The k<sup>1</sup> compounds can therefore be trapped by treating the k<sup>2</sup> isomers with <i>tris</i>-pentafluorophenyl borane.

scholarly journals Scandium Alkyl and Hydride Complexes Supported by a Pentadentate Diborate Ligand: Reactions with CO2 and N2O

2018 ◽  
Author(s):  
Warren Piers ◽  
Daniel W. Beh ◽  
Iker del Rosal ◽  
Maron Laurent ◽  
Benjamin S. Gelfand ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Slow Rate ◽  
Function Theory ◽  
Density Function Theory ◽  
Insertion Reactions ◽  
Hydride Complexes ◽  
Alkyl Derivatives ◽  
Organolithium Reagents ◽  
Rate Of Reaction ◽  
Sigma Bond

Alkyl and hydrido scandium complexes of the dianionic pentatdentate ligand B<sub>2</sub>Pz<sub>4</sub>Py are reported. The key starting material (B<sub>2</sub>Pz<sub>4</sub>Py)ScCl is readily prepared and alkylated with organolithium reagents RLi (R = CH<sub>3</sub>, CH<sub>2</sub>SiMe<sub>3</sub>, CH<sub>2</sub>SiMe<sub>2</sub>Ph, CH<sub>2</sub>CH<sub>2</sub>CH<sub>3</sub> and CH<sub>2</sub>CHMe<sub>2</sub>) to form alkyl derivatives in 61-93% yields. These compounds are very thermally stable and do not undergo sigma bond metathesis reactions with dihydrogen. The hydrido complex was prepared from (B<sub>2</sub>Pz<sub>4</sub>Py)ScCl and NaHBEt<sub>3</sub> in 80% yield and was found to be more stable by 28 kcal mol<sup>-1</sup> as a dimer, rather than a monomeric hydrido complex. However, the monomer is accessible through dissociation of the dimer at 80˚C. All of the compounds (B<sub>2</sub>Pz<sub>4</sub>Py)ScR react with water to form the bridging oxo dimer (B<sub>2</sub>Pz<sub>4</sub>Py)ScOSc(B<sub>2</sub>Pz<sub>4</sub>Py). The reactivity of the hydrido and methyl complexes towards carbon dioxide was explored; heating to 80˚C results in the formation of k<sup>2</sup> formato and acetate complexes, respectively. The mechanisms were studied via density function theory and distinct transition states for insertion of CO<sub>2</sub> into the Sc-R (R = H, CH<sub>3</sub>) were found, with the insertion into the Sc-CH<sub>3</sub> being more enthalpically difficult (by 18 kcal mol<sup>-1</sup>) than insertion into Sc-H. The slow rate of reaction between [(B<sub>2</sub>Pz<sub>4</sub>Py)ScH]<sub>2</sub> and CO<sub>2</sub> is attributed to the barrier associated with dimer dissociation. In both insertion reactions, the kinetic products are k<sup>1</sup> formato or acetate complexes that are only slightly less stable than the observed k<sup>2</sup> derivatives. The k<sup>1</sup> compounds can therefore be trapped by treating the k<sup>2</sup> isomers with <i>tris</i>-pentafluorophenyl borane.

ChemInform Abstract: STRUCTURE OF THE PRODUCT FORMED IN THE REACTION OF CARBON DIOXIDE WITH RUTHENIUM HYDRIDE COMPLEXES

1974 ◽  
Vol 5 (4) ◽  
pp. no-no
Author(s):  
I. S. KOLOMNIKOV ◽  
A. I. GUSEV ◽  
G. G. ALEKSANDROV ◽  
T. S. LOBEEVA ◽  
YU. T. STRUCHKOV ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Ruthenium Hydride ◽  
Hydride Complexes ◽  
Abstract Structure

Efficient Reduction of Carbon Dioxide to Methanol Equivalents Catalyzed by Two-Coordinate Amido–Germanium(II) and −Tin(II) Hydride Complexes

ACS Catalysis ◽  
2017 ◽  
Vol 7 (3) ◽  
pp. 1853-1859 ◽  
Author(s):  
Terrance J. Hadlington ◽  
Christos E. Kefalidis ◽  
Laurent Maron ◽  
Cameron Jones
Keyword(s):  
Carbon Dioxide ◽  
Hydride Complexes ◽  
Efficient Reduction

Structure of the product formed in the reaction of carbon dioxide with ruthenium hydride complexes

1973 ◽  
Vol 59 ◽  
pp. 349-351 ◽  
Author(s):  
I.S. Kolomnikov ◽  
A.I. Gusev ◽  
G.G. Aleksandrov ◽  
T.S. Lobeeva ◽  
Yu T. Struchkov ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Ruthenium Hydride ◽  
Hydride Complexes
Sign in / Sign up

Export Citation Format

Share Document