Synthesis, Reactivity, and Ligand Dynamics of Ru3(CO)9(μ−CO) (μ3−η2−alkyne) Compounds

Silvio Aime; Roberto Gobetto; Luciano Milone; Domenico Osella; Luciana Violano; Alejandro J. Arce; Ysaura De Sanctis

doi:10.1021/om00054a060

Synthesis, Reactivity, and Ligand Dynamics of Ru₃(CO)₉(μ−CO) (μ₃−η²−alkyne) Compounds

Silvio Aime, Roberto Gobetto, Luciano Milone, Domenico Osella, Luciana Violano, Alejandro J. Arce, Ysaura De Sanctis

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

Abstract

Acetylene, terminal HC₂R (R = COOH, CHO), and nonterminal RC₂R (R = Et, CH₂OH, Ph) alkynes react at room temperature with Ru₃(CO)₁₀(MeCN)₂ to give almost quantitatively Ru₃(CO)₉(μ−CO)(μ₃− η²−alkyne) compounds, which are shown to be the precursors of the acetylides Ru₃(CO)₉(μ−H)(C₂R) in the case of acetylene and of terminal alkynes or of the allenic Ru₃(CO)₉(μ−H)(RC=C=CR′R″) complexes in the case of internal alkynes. Ru₃(CO)₉(μ−CO)(C₂H₂) at room temperature adds H₂ to give Ru₃(CO)₉(μ− H)₂(HC=CH), which is further hydrogenated at 3 atm to give Ru₃(CO)₉(μ−H)₃CCH₃. Ru₃(CO)₉(μ−CO)(C₂H₂) is stereochemically nonrigid: A low-energy process averages, on the NMR time scale, the semibridging CO with two pairs of terminal carbonyls at the bridged Ru atoms, and it is coupled to an alternate lengthening of one of the Ru−C σ bonds at the same metal atoms. At high temperature, all the carbonyls are equivalent.

Original language	English
Pages (from-to)	2854-2856
Number of pages	3
Journal	Organometallics
Volume	10
Issue number	8
DOIs	https://doi.org/10.1021/om00054a060
Publication status	Published - 1 Aug 1991
Externally published	Yes

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title = "Synthesis, Reactivity, and Ligand Dynamics of Ru3(CO)9(μ−CO) (μ3−η2−alkyne) Compounds",

abstract = "Acetylene, terminal HC2R (R = COOH, CHO), and nonterminal RC2R (R = Et, CH2OH, Ph) alkynes react at room temperature with Ru3(CO)10(MeCN)2 to give almost quantitatively Ru3(CO)9(μ−CO)(μ3− η2−alkyne) compounds, which are shown to be the precursors of the acetylides Ru3(CO)9(μ−H)(C2R) in the case of acetylene and of terminal alkynes or of the allenic Ru3(CO)9(μ−H)(RC=C=CR′R″) complexes in the case of internal alkynes. Ru3(CO)9(μ−CO)(C2H2) at room temperature adds H2 to give Ru3(CO)9(μ− H)2(HC=CH), which is further hydrogenated at 3 atm to give Ru3(CO)9(μ−H)3CCH3. Ru3(CO)9(μ−CO)(C2H2) is stereochemically nonrigid: A low-energy process averages, on the NMR time scale, the semibridging CO with two pairs of terminal carbonyls at the bridged Ru atoms, and it is coupled to an alternate lengthening of one of the Ru−C σ bonds at the same metal atoms. At high temperature, all the carbonyls are equivalent.",

author = "Silvio Aime and Roberto Gobetto and Luciano Milone and Domenico Osella and Luciana Violano and Arce, {Alejandro J.} and Sanctis, {Ysaura De}",

year = "1991",

month = aug,

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doi = "10.1021/om00054a060",

language = "English",

volume = "10",

pages = "2854--2856",

journal = "Organometallics",

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T1 - Synthesis, Reactivity, and Ligand Dynamics of Ru3(CO)9(μ−CO) (μ3−η2−alkyne) Compounds

AU - Aime, Silvio

AU - Gobetto, Roberto

AU - Milone, Luciano

AU - Osella, Domenico

AU - Violano, Luciana

AU - Arce, Alejandro J.

AU - Sanctis, Ysaura De

PY - 1991/8/1

Y1 - 1991/8/1

N2 - Acetylene, terminal HC2R (R = COOH, CHO), and nonterminal RC2R (R = Et, CH2OH, Ph) alkynes react at room temperature with Ru3(CO)10(MeCN)2 to give almost quantitatively Ru3(CO)9(μ−CO)(μ3− η2−alkyne) compounds, which are shown to be the precursors of the acetylides Ru3(CO)9(μ−H)(C2R) in the case of acetylene and of terminal alkynes or of the allenic Ru3(CO)9(μ−H)(RC=C=CR′R″) complexes in the case of internal alkynes. Ru3(CO)9(μ−CO)(C2H2) at room temperature adds H2 to give Ru3(CO)9(μ− H)2(HC=CH), which is further hydrogenated at 3 atm to give Ru3(CO)9(μ−H)3CCH3. Ru3(CO)9(μ−CO)(C2H2) is stereochemically nonrigid: A low-energy process averages, on the NMR time scale, the semibridging CO with two pairs of terminal carbonyls at the bridged Ru atoms, and it is coupled to an alternate lengthening of one of the Ru−C σ bonds at the same metal atoms. At high temperature, all the carbonyls are equivalent.

AB - Acetylene, terminal HC2R (R = COOH, CHO), and nonterminal RC2R (R = Et, CH2OH, Ph) alkynes react at room temperature with Ru3(CO)10(MeCN)2 to give almost quantitatively Ru3(CO)9(μ−CO)(μ3− η2−alkyne) compounds, which are shown to be the precursors of the acetylides Ru3(CO)9(μ−H)(C2R) in the case of acetylene and of terminal alkynes or of the allenic Ru3(CO)9(μ−H)(RC=C=CR′R″) complexes in the case of internal alkynes. Ru3(CO)9(μ−CO)(C2H2) at room temperature adds H2 to give Ru3(CO)9(μ− H)2(HC=CH), which is further hydrogenated at 3 atm to give Ru3(CO)9(μ−H)3CCH3. Ru3(CO)9(μ−CO)(C2H2) is stereochemically nonrigid: A low-energy process averages, on the NMR time scale, the semibridging CO with two pairs of terminal carbonyls at the bridged Ru atoms, and it is coupled to an alternate lengthening of one of the Ru−C σ bonds at the same metal atoms. At high temperature, all the carbonyls are equivalent.

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U2 - 10.1021/om00054a060

DO - 10.1021/om00054a060

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ER -

Synthesis, Reactivity, and Ligand Dynamics of Ru₃(CO)₉(μ−CO) (μ₃−η²−alkyne) Compounds

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