Reactions of Protic Acids with a Hydridoorganometal Cluster: HRu3(CO)9(C2C(CH3)3)

Claudia Barner-Thorsen; Edward Rosenberg; Gloria Saatjian; Silvio Aime; Luciano Milone; Domenico Osella

doi:10.1021/ic50219a051

Reactions of Protic Acids with a Hydridoorganometal Cluster: HRu₃(CO)₉(C₂C(CH₃)₃)

Claudia Barner-Thorsen, Edward Rosenberg, Gloria Saatjian, Silvio Aime, Luciano Milone, Domenico Osella

Risultato della ricerca: Contributo su rivista › Articolo in rivista › peer review

Abstract

The titrations of HRu₃(CO)₉C₆H₉ (I), HRu₃(CO)₈(C₆H₉)PR₃ (R = C₆H₅, OCH₃) (II), and HRu₃(CO)₇(C₆H₉)(PR₃)₂ (R = C₆H₅, OCH₃) (III) with CF₃S0₃H in CD₂C1₂ have been followed by variable-temperature ¹H NMR. Initial protonation takes place at the metal core, but significant differences in the relative basicities and the rates of inter- and m/ramolecular hydride exchange are observed. In neat sulfuric acid a second protonation of I takes place at the organic ligand to yield a dicationic dihydrido complex H₂Ru₃(CO)₉(HC=CC(CH₃)₃)²⁺. In the case of II two isomeric dications are obtained as kinetic products with subsequent rearrangement to the more thermodynamically stable isomer. In D₂S0₄ gives only the more thermodynamically stable product white deuterated II in H2S04 gives a different isomer ratio than II in H₂S0₄. A mechanism explaining this unusual deuterium isotope effect is presented and discussed.

Lingua originale	Inglese
pagine (da-a)	1592-1597
Numero di pagine	6
Rivista	Inorganic Chemistry
Volume	20
Numero di pubblicazione	5
DOI	https://doi.org/10.1021/ic50219a051
Stato di pubblicazione	Pubblicato - mag 1981
Pubblicato esternamente	Sì

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10.1021/ic50219a051

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@article{33a4af15d0614820998e5a7c74720d8f,

title = "Reactions of Protic Acids with a Hydridoorganometal Cluster: HRu3(CO)9(C2C(CH3)3)",

abstract = "The titrations of HRu3(CO)9C6H9 (I), HRu3(CO)8(C6H9)PR3 (R = C6H5, OCH3) (II), and HRu3(CO)7(C6H9)(PR3)2 (R = C6H5, OCH3) (III) with CF3S03H in CD2C12 have been followed by variable-temperature 1H NMR. Initial protonation takes place at the metal core, but significant differences in the relative basicities and the rates of inter- and m/ramolecular hydride exchange are observed. In neat sulfuric acid a second protonation of I takes place at the organic ligand to yield a dicationic dihydrido complex H2Ru3(CO)9(HC=CC(CH3)3)2+. In the case of II two isomeric dications are obtained as kinetic products with subsequent rearrangement to the more thermodynamically stable isomer. In D2S04 gives only the more thermodynamically stable product white deuterated II in H2S04 gives a different isomer ratio than II in H2S04. A mechanism explaining this unusual deuterium isotope effect is presented and discussed.",

author = "Claudia Barner-Thorsen and Edward Rosenberg and Gloria Saatjian and Silvio Aime and Luciano Milone and Domenico Osella",

year = "1981",

month = may,

doi = "10.1021/ic50219a051",

language = "English",

volume = "20",

pages = "1592--1597",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "5",

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T1 - Reactions of Protic Acids with a Hydridoorganometal Cluster

T2 - HRu3(CO)9(C2C(CH3)3)

AU - Barner-Thorsen, Claudia

AU - Rosenberg, Edward

AU - Saatjian, Gloria

AU - Aime, Silvio

AU - Milone, Luciano

AU - Osella, Domenico

PY - 1981/5

Y1 - 1981/5

N2 - The titrations of HRu3(CO)9C6H9 (I), HRu3(CO)8(C6H9)PR3 (R = C6H5, OCH3) (II), and HRu3(CO)7(C6H9)(PR3)2 (R = C6H5, OCH3) (III) with CF3S03H in CD2C12 have been followed by variable-temperature 1H NMR. Initial protonation takes place at the metal core, but significant differences in the relative basicities and the rates of inter- and m/ramolecular hydride exchange are observed. In neat sulfuric acid a second protonation of I takes place at the organic ligand to yield a dicationic dihydrido complex H2Ru3(CO)9(HC=CC(CH3)3)2+. In the case of II two isomeric dications are obtained as kinetic products with subsequent rearrangement to the more thermodynamically stable isomer. In D2S04 gives only the more thermodynamically stable product white deuterated II in H2S04 gives a different isomer ratio than II in H2S04. A mechanism explaining this unusual deuterium isotope effect is presented and discussed.

AB - The titrations of HRu3(CO)9C6H9 (I), HRu3(CO)8(C6H9)PR3 (R = C6H5, OCH3) (II), and HRu3(CO)7(C6H9)(PR3)2 (R = C6H5, OCH3) (III) with CF3S03H in CD2C12 have been followed by variable-temperature 1H NMR. Initial protonation takes place at the metal core, but significant differences in the relative basicities and the rates of inter- and m/ramolecular hydride exchange are observed. In neat sulfuric acid a second protonation of I takes place at the organic ligand to yield a dicationic dihydrido complex H2Ru3(CO)9(HC=CC(CH3)3)2+. In the case of II two isomeric dications are obtained as kinetic products with subsequent rearrangement to the more thermodynamically stable isomer. In D2S04 gives only the more thermodynamically stable product white deuterated II in H2S04 gives a different isomer ratio than II in H2S04. A mechanism explaining this unusual deuterium isotope effect is presented and discussed.

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U2 - 10.1021/ic50219a051

DO - 10.1021/ic50219a051

M3 - Article

SN - 0020-1669

VL - 20

SP - 1592

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 5