Redox Behavior of the Electronically Unsaturated Clusters Os3(μ-H)2(CO)9L and Their Saturated Congeners Os3(μ-H)(H)(CO)10L (L = CO, PPh3, AsPh3)

Domenico Osella; Edison Stein; Carlo Nervi; Piero Zanello; Franco Laschi; Arnaldo Cinquantini; Edward Rosenberg; Jan Fiedler

doi:10.1021/om00052a045

Redox Behavior of the Electronically Unsaturated Clusters Os₃(μ-H)₂(CO)₉L and Their Saturated Congeners Os₃(μ-H)(H)(CO)₁₀L (L = CO, PPh₃, AsPh₃)

Domenico Osella
, Edison Stein
, Carlo Nervi
, Piero Zanello
, Franco Laschi
, Arnaldo Cinquantini
, Edward Rosenberg
, Jan Fiedler

Research output: Contribution to journal › Article › peer-review

Abstract

The 46 e cluster Os₃(μ-H)₂(CO)₁₀ exhibits a very complex redox behavior. Its cyclic voltammetric (CV) response consists of two reduction peaks, the latter having an adsorption character. Polarographic, coulometric, and spectroscopic data indicate that the initially electrogenerated monoanion [Os₃H₂(CO)₁₀]⁻ undergoes several chemical side reactions, one being an irreversible cluster breakdown and the others being dimerization reactions. The adducts Os₃(H)(μ-H)(CO)₁₀L with Lewis bases (L = CO, PPh₃, AsPh₃) exhibit a single 2e, chemically irreversible reduction process at more negative potentials than Os₃H₂(CO)₁₀. Their electrochemical behavior is similar to that of the saturated cluster Os₃(CO)₁₂. Elimination of one CO on thermolysis produces Os₃H₂(CO)₉L (L = PPh₃, AsPh₃) where the unsaturated system Os-H₂-Os is restored; accordingly its CV response is very similar to that of the parent compound, Os₃H₂(CO)₁₀.

Original language	English
Pages (from-to)	1929-1934
Number of pages	6
Journal	Organometallics
Volume	10
Issue number	6
DOIs	https://doi.org/10.1021/om00052a045
Publication status	Published - 1 Jun 1991
Externally published	Yes

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title = "Redox Behavior of the Electronically Unsaturated Clusters Os3(μ-H)2(CO)9L and Their Saturated Congeners Os3(μ-H)(H)(CO)10L (L = CO, PPh3, AsPh3)",

abstract = "The 46 e cluster Os3(μ-H)2(CO)10 exhibits a very complex redox behavior. Its cyclic voltammetric (CV) response consists of two reduction peaks, the latter having an adsorption character. Polarographic, coulometric, and spectroscopic data indicate that the initially electrogenerated monoanion [Os3H2(CO)10]− undergoes several chemical side reactions, one being an irreversible cluster breakdown and the others being dimerization reactions. The adducts Os3(H)(μ-H)(CO)10L with Lewis bases (L = CO, PPh3, AsPh3) exhibit a single 2e, chemically irreversible reduction process at more negative potentials than Os3H2(CO)10. Their electrochemical behavior is similar to that of the saturated cluster Os3(CO)12. Elimination of one CO on thermolysis produces Os3H2(CO)9L (L = PPh3, AsPh3) where the unsaturated system Os-H2-Os is restored; accordingly its CV response is very similar to that of the parent compound, Os3H2(CO)10.",

author = "Domenico Osella and Edison Stein and Carlo Nervi and Piero Zanello and Franco Laschi and Arnaldo Cinquantini and Edward Rosenberg and Jan Fiedler",

year = "1991",

month = jun,

day = "1",

doi = "10.1021/om00052a045",

language = "English",

volume = "10",

pages = "1929--1934",

journal = "Organometallics",

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TY - JOUR

T1 - Redox Behavior of the Electronically Unsaturated Clusters Os3(μ-H)2(CO)9L and Their Saturated Congeners Os3(μ-H)(H)(CO)10L (L = CO, PPh3, AsPh3)

AU - Osella, Domenico

AU - Stein, Edison

AU - Nervi, Carlo

AU - Zanello, Piero

AU - Laschi, Franco

AU - Cinquantini, Arnaldo

AU - Rosenberg, Edward

AU - Fiedler, Jan

PY - 1991/6/1

Y1 - 1991/6/1

N2 - The 46 e cluster Os3(μ-H)2(CO)10 exhibits a very complex redox behavior. Its cyclic voltammetric (CV) response consists of two reduction peaks, the latter having an adsorption character. Polarographic, coulometric, and spectroscopic data indicate that the initially electrogenerated monoanion [Os3H2(CO)10]− undergoes several chemical side reactions, one being an irreversible cluster breakdown and the others being dimerization reactions. The adducts Os3(H)(μ-H)(CO)10L with Lewis bases (L = CO, PPh3, AsPh3) exhibit a single 2e, chemically irreversible reduction process at more negative potentials than Os3H2(CO)10. Their electrochemical behavior is similar to that of the saturated cluster Os3(CO)12. Elimination of one CO on thermolysis produces Os3H2(CO)9L (L = PPh3, AsPh3) where the unsaturated system Os-H2-Os is restored; accordingly its CV response is very similar to that of the parent compound, Os3H2(CO)10.

AB - The 46 e cluster Os3(μ-H)2(CO)10 exhibits a very complex redox behavior. Its cyclic voltammetric (CV) response consists of two reduction peaks, the latter having an adsorption character. Polarographic, coulometric, and spectroscopic data indicate that the initially electrogenerated monoanion [Os3H2(CO)10]− undergoes several chemical side reactions, one being an irreversible cluster breakdown and the others being dimerization reactions. The adducts Os3(H)(μ-H)(CO)10L with Lewis bases (L = CO, PPh3, AsPh3) exhibit a single 2e, chemically irreversible reduction process at more negative potentials than Os3H2(CO)10. Their electrochemical behavior is similar to that of the saturated cluster Os3(CO)12. Elimination of one CO on thermolysis produces Os3H2(CO)9L (L = PPh3, AsPh3) where the unsaturated system Os-H2-Os is restored; accordingly its CV response is very similar to that of the parent compound, Os3H2(CO)10.

UR - https://www.scopus.com/pages/publications/0040375909

U2 - 10.1021/om00052a045

DO - 10.1021/om00052a045

M3 - Article

SN - 0276-7333

VL - 10

SP - 1929

EP - 1934

JO - Organometallics

JF - Organometallics

IS - 6

ER -

Redox Behavior of the Electronically Unsaturated Clusters Os₃(μ-H)₂(CO)₉L and Their Saturated Congeners Os₃(μ-H)(H)(CO)₁₀L (L = CO, PPh₃, AsPh₃)

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