Classical, nonclassical, and mixed-metal osmium(II) polyhydrides stabilized by the tetraphosphine P(CH2CH2PPh2)3. Hydrogen/deuterium isotope exchange reactions promoted by a strongly bound dihydrogen ligand

Bianchini, Claudio; Linn, Klaus; Masi, Dante; Peruzzini, Maurizio; Polo, A.; Vacca, Alberto; Zanobini, Fabrizio

doi:10.1021/ic00063a028

Cited by 65 publications

(50 citation statements)

References 4 publications

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“…IR and Raman assignment of the ν MH bands in 1 – 3 : The solid‐state IR spectra of 1 – 3 showed two intense ν MH absorptions in the region between 1950 and 1730 cm −1 4a–4e. Similar bands were found in the IR spectra recorded in either CH 2 Cl 2 or THF solution (Table 2).…”

Section: Resultssupporting

confidence: 62%

“…Indeed, these Group 8 dihydrides constitute a family of octahedral transition‐metal complexes sharing an identical ligand environment as well as reactivity towards Brønsted acids 4. The latter can transform the dihydrides into cationic dihydrogen complexes [M(H)(H 2 )(PP 3 )]X with no change of the metal oxidation state [M=Fe, ( 4 ); Ru, ( 5 ); Os ( 6 ); X=non‐coordinating counter‐anion] (Scheme ) 4a–4e…”

Section: Introductionmentioning

confidence: 99%

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Low‐Temperature IR and NMR Studies of the Interaction of Group 8 Metal Dihydrides with Alcohols

Gutsul

Belkova

Sverdlov

et al. 2003

Chemistry A European J

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The reactions of the octahedral dihydrido complexes [MH(2)(PP(3))] [M=Fe, Ru, Os; PP(3)=P(CH(2)CH(2)PPh(2))(3)] with a variety of weak ROH acids have been studied by IR and NMR methods in either CH(2)Cl(2) or THF in the temperature range from 190 to 290 K. This study has allowed the determination of the spectral and thermodynamic properties associated with the formation of dihydrogen bonds (DHB) between the terminal hydrides and the OH group. Both the DHB enthalpy values and the hydride basicity factors (E(j)) have been found to increase in the order Fe < Ru < Os. The proton transfer process, leading to the DHB complexes, and eventually to eta(2)-H(2) products, has been found to depend on the acidic strength of the alcohol as well as the nature of the solvent. Low temperature IR and NMR techniques have been used to trace the complete energy profile of the proton transfer process involving the osmium complex [OsH(2)(PP(3))] with trifluoroethanol.

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Section: Resultssupporting

confidence: 62%

Section: Introductionmentioning

confidence: 99%

Low‐Temperature IR and NMR Studies of the Interaction of Group 8 Metal Dihydrides with Alcohols

Gutsul

Belkova

Sverdlov

et al. 2003

Chemistry A European J

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“…Possible mechanisms could involve 7-or 8-coordinate 20e intermediates such as a (H 2 )(D 2 ) complex or species such as WH 2 (D 2 )(CO) 3 (PR 3 ) 2 , but no evidence exists for these. Trace quantities of adventitious water may lead to exchange since isotopic scrambling of W(CO) 3 (PR 3 ) 2 (D 2 ) with H 2 O occurs in solution within days [85] or less for other D 2 complexes [86][87][88][89][90][91][92]. A reasonable exchange mechanism for complexes with one open coordination site is deprotonation of g 2 -H 2 by the weak base water followed by reprotonation with H 2 DO + .…”

Section: Catalysis Of Isotopic Exchange By H 2 Complexesmentioning

confidence: 99%

“…reaction of acetone-d 6 and [RuCl(dppe) 2 (H 2 )] + or [OsH(H 2 )(PP 3 )] + gives the HD isotopomer in 20 min and the fully deuterated complexes in a few hours [87,97].…”

Section: Catalysis Of Isotopic Exchange By H 2 Complexesmentioning

confidence: 99%

Catalytic Processes Involving Dihydrogen Complexes and Other Sigma-bond Complexes

Kubas

2005

Catal Lett

109

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“…[8a] However, to the best of our knowledge, complexes 3 ± 5 are the first examples of a double protonation of a symmetric binuclear complex leading to an asymmetric species. [17,24] and attributed to the acidity of the hydride complexes. [25] In agreement with this proposal, 2 can be readily deprotonated by NEt 3 to yield 1.…”

mentioning

confidence: 99%

Binuclear Oxidative Addition of Hydrogen in Diamidonaphthalene‐Bridged Diiridium Complexes

Jiménez

Sola

López

et al. 1998

Chemistry A European J

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) (7 a, 7 b), in which a molecule of hydrogen has been added to form a terminal and a bridging hydride. In the presence of NEt 3 , 7 a and 7 b isomerize into the symmetric complex 8 which presents a trans arrangement of the hydrides. Oxidation of complex 1 allows the preparation of the iridium(ii) species [Ir 2 (m-1,8-(NH) 2 naphth)(OSO 2 CF 3 ) 2 -(CO) 2 (PiPr 3 ) 2 ] (9). The triflate ligands of 9 can be replaced by tetrahydrothiophene or acetonitrile to give complexes 10 and 11, respectively. The acetonitrile complexes can exist as three different isomers: two have C 2 symmetry (11 a, 11 c) and one is asymmetric (11 b); the latter has been characterized by X-ray diffraction. The kinetic study of the isomerization reactions reveals these processes to be strictly intramolecular. The reaction of 9 with hydrogen gives different final products, depending on the solvent. Thus, in CDCl 3 the dihydride 3 is obtained, whereas in acetone a mixture of the trihydrides 7 a and 7 b is formed.

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Classical, nonclassical, and mixed-metal osmium(II) polyhydrides stabilized by the tetraphosphine P(CH2CH2PPh2)3. Hydrogen/deuterium isotope exchange reactions promoted by a strongly bound dihydrogen ligand

Cited by 65 publications

References 4 publications

Low‐Temperature IR and NMR Studies of the Interaction of Group 8 Metal Dihydrides with Alcohols

Low‐Temperature IR and NMR Studies of the Interaction of Group 8 Metal Dihydrides with Alcohols

Catalytic Processes Involving Dihydrogen Complexes and Other Sigma-bond Complexes

Binuclear Oxidative Addition of Hydrogen in Diamidonaphthalene‐Bridged Diiridium Complexes

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