Comparative Reactivity of Triruthenium and Triosmium µ3-h2-Imidoyls, Part 2: Reactions with Alkynes

Kabir SE; E Rosenberg; L Milone; R Gobetto; Domenico OSELLA; Mauro RAVERA; T McPhillips; Day MW; D Carlot; S Hajela; E Wolf; K. Hardcastle

doi:10.1021/om9610915

Comparative Reactivity of Triruthenium and Triosmium µ3-h2-Imidoyls, Part 2: Reactions with Alkynes

Kabir SE, E Rosenberg, L Milone, R Gobetto, Domenico OSELLA, Mauro RAVERA, T McPhillips, Day MW, D Carlot, S Hajela, E Wolf, K. Hardcastle

Dipartimento di Scienze e Innovazione Tecnologica

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

Abstract

The reactions of Ru₃(CO)₉(μ₃-η²-CH ₃C=NCH₂CH₃)(μ-H) (1), M₃(CO)₉(μ₃-η²-C=N(CH ₂)₃)(μ-H) (M = Ru (2), M = Os (3)) with the alkynes RC≡CR (R = CH₃, C₆H₅, CO₂Me) have been studied. The ruthenium complexes 1 and 2 react with 2-butyne at 70 °C to give two very different trimetallic alkyne derivatives: Ru₃(CO)₇(μ-η²:η⁴-C ₄(CH₃)₄)(μ-η²-CH ₃C=NCH₂CH₃)-(η¹-COC(CH ₃)C(H)CH₃ (5) and Ru₃(CO)₈(μ₃-η²-C=N(CH ₂)₃)(μ-η²-CH₃C(H)=CCH ₃) (6). The osmium imidoyl 3 does not react with 2-butyne even at elevated temperatures. However, the reaction of Os₃(CO)₉(μ-η²-C=N(CH₂) ₃)(μ-H)(CH₃CN) (7b), synthesized from Os₃(CO)₁₀-(μ-η²-C=N(CH₂) ₃)(μ-H) (7a), with 2-butyne yields the analog of 6, Os₃(CO)₈(μ₃-η²-C=N(CH ₂)³)(μ-η²-RC(H)=CR) (R = CH₃ (10), R = C₆H₅ (11)) on thermolysis of the initially formed nonacarbonyl precursors (8 and 9 for R = CH₃), which are a mixture of isomers. Direct reaction of 7a with diphenylacetylene at 100 °C gives somewhat lower yields of 11. The reaction of 7b with dimethylacetylenedicarboxylate or the direct reaction of 3 with this alkyne yields the nonacarbonyl derivative Os₃(CO)₉(μ-η²-C=N(CH₂) ₃)(μ₃-η³-CH₃O ₂CC=C(H)CO₂CH₃) (12). Direct reaction of 7a with a 2.5 molar excess trimethylamine N-oxide at room temperature yields the alkyne-imidoyl-coupled product Os₃(CO)₈(μ-η⁶-CH ₃C(H)=C(CH₃)C-(CH₃)=C(CH ₃)C=N(CH₂)₃) (13). The solid state structures of 5, 11, 12, and 13 are reported. A comparative study of the electrochemical properties of 5 and 1 is also reported.

Lingua originale	Inglese
pagine (da-a)	2674-2681
Numero di pagine	8
Rivista	Organometallics
Volume	16
Numero di pubblicazione	12
DOI	https://doi.org/10.1021/om9610915
Stato di pubblicazione	Pubblicato - 1997

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10.1021/om9610915

http://hdl.handle.net/11579/32871

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@article{bc94bce722094e808c3a6fa8769e23aa,

title = "Comparative Reactivity of Triruthenium and Triosmium µ3-h2-Imidoyls, Part 2: Reactions with Alkynes",

abstract = "The reactions of Ru3(CO)9(μ3-η2-CH 3C=NCH2CH3)(μ-H) (1), M3(CO)9(μ3-η2-C=N(CH 2)3)(μ-H) (M = Ru (2), M = Os (3)) with the alkynes RC≡CR (R = CH3, C6H5, CO2Me) have been studied. The ruthenium complexes 1 and 2 react with 2-butyne at 70 °C to give two very different trimetallic alkyne derivatives: Ru3(CO)7(μ-η2:η4-C 4(CH3)4)(μ-η2-CH 3C=NCH2CH3)-(η1-COC(CH 3)C(H)CH3 (5) and Ru3(CO)8(μ3-η2-C=N(CH 2)3)(μ-η2-CH3C(H)=CCH 3) (6). The osmium imidoyl 3 does not react with 2-butyne even at elevated temperatures. However, the reaction of Os3(CO)9(μ-η2-C=N(CH2) 3)(μ-H)(CH3CN) (7b), synthesized from Os3(CO)10-(μ-η2-C=N(CH2) 3)(μ-H) (7a), with 2-butyne yields the analog of 6, Os3(CO)8(μ3-η2-C=N(CH 2)3)(μ-η2-RC(H)=CR) (R = CH3 (10), R = C6H5 (11)) on thermolysis of the initially formed nonacarbonyl precursors (8 and 9 for R = CH3), which are a mixture of isomers. Direct reaction of 7a with diphenylacetylene at 100 °C gives somewhat lower yields of 11. The reaction of 7b with dimethylacetylenedicarboxylate or the direct reaction of 3 with this alkyne yields the nonacarbonyl derivative Os3(CO)9(μ-η2-C=N(CH2) 3)(μ3-η3-CH3O 2CC=C(H)CO2CH3) (12). Direct reaction of 7a with a 2.5 molar excess trimethylamine N-oxide at room temperature yields the alkyne-imidoyl-coupled product Os3(CO)8(μ-η6-CH 3C(H)=C(CH3)C-(CH3)=C(CH 3)C=N(CH2)3) (13). The solid state structures of 5, 11, 12, and 13 are reported. A comparative study of the electrochemical properties of 5 and 1 is also reported.",

author = "Kabir SE and E Rosenberg and L Milone and R Gobetto and Domenico OSELLA and Mauro RAVERA and T McPhillips and Day MW and D Carlot and S Hajela and E Wolf and K. Hardcastle",

year = "1997",

doi = "10.1021/om9610915",

language = "English",

volume = "16",

pages = "2674--2681",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Comparative Reactivity of Triruthenium and Triosmium µ3-h2-Imidoyls, Part 2: Reactions with Alkynes

AU - SE, Kabir

AU - Rosenberg, E

AU - Milone, L

AU - Gobetto, R

AU - OSELLA, Domenico

AU - RAVERA, Mauro

AU - McPhillips, T

AU - MW, Day

AU - Carlot, D

AU - Hajela, S

AU - Wolf, E

AU - Hardcastle, K.

PY - 1997

Y1 - 1997

N2 - The reactions of Ru3(CO)9(μ3-η2-CH 3C=NCH2CH3)(μ-H) (1), M3(CO)9(μ3-η2-C=N(CH 2)3)(μ-H) (M = Ru (2), M = Os (3)) with the alkynes RC≡CR (R = CH3, C6H5, CO2Me) have been studied. The ruthenium complexes 1 and 2 react with 2-butyne at 70 °C to give two very different trimetallic alkyne derivatives: Ru3(CO)7(μ-η2:η4-C 4(CH3)4)(μ-η2-CH 3C=NCH2CH3)-(η1-COC(CH 3)C(H)CH3 (5) and Ru3(CO)8(μ3-η2-C=N(CH 2)3)(μ-η2-CH3C(H)=CCH 3) (6). The osmium imidoyl 3 does not react with 2-butyne even at elevated temperatures. However, the reaction of Os3(CO)9(μ-η2-C=N(CH2) 3)(μ-H)(CH3CN) (7b), synthesized from Os3(CO)10-(μ-η2-C=N(CH2) 3)(μ-H) (7a), with 2-butyne yields the analog of 6, Os3(CO)8(μ3-η2-C=N(CH 2)3)(μ-η2-RC(H)=CR) (R = CH3 (10), R = C6H5 (11)) on thermolysis of the initially formed nonacarbonyl precursors (8 and 9 for R = CH3), which are a mixture of isomers. Direct reaction of 7a with diphenylacetylene at 100 °C gives somewhat lower yields of 11. The reaction of 7b with dimethylacetylenedicarboxylate or the direct reaction of 3 with this alkyne yields the nonacarbonyl derivative Os3(CO)9(μ-η2-C=N(CH2) 3)(μ3-η3-CH3O 2CC=C(H)CO2CH3) (12). Direct reaction of 7a with a 2.5 molar excess trimethylamine N-oxide at room temperature yields the alkyne-imidoyl-coupled product Os3(CO)8(μ-η6-CH 3C(H)=C(CH3)C-(CH3)=C(CH 3)C=N(CH2)3) (13). The solid state structures of 5, 11, 12, and 13 are reported. A comparative study of the electrochemical properties of 5 and 1 is also reported.

AB - The reactions of Ru3(CO)9(μ3-η2-CH 3C=NCH2CH3)(μ-H) (1), M3(CO)9(μ3-η2-C=N(CH 2)3)(μ-H) (M = Ru (2), M = Os (3)) with the alkynes RC≡CR (R = CH3, C6H5, CO2Me) have been studied. The ruthenium complexes 1 and 2 react with 2-butyne at 70 °C to give two very different trimetallic alkyne derivatives: Ru3(CO)7(μ-η2:η4-C 4(CH3)4)(μ-η2-CH 3C=NCH2CH3)-(η1-COC(CH 3)C(H)CH3 (5) and Ru3(CO)8(μ3-η2-C=N(CH 2)3)(μ-η2-CH3C(H)=CCH 3) (6). The osmium imidoyl 3 does not react with 2-butyne even at elevated temperatures. However, the reaction of Os3(CO)9(μ-η2-C=N(CH2) 3)(μ-H)(CH3CN) (7b), synthesized from Os3(CO)10-(μ-η2-C=N(CH2) 3)(μ-H) (7a), with 2-butyne yields the analog of 6, Os3(CO)8(μ3-η2-C=N(CH 2)3)(μ-η2-RC(H)=CR) (R = CH3 (10), R = C6H5 (11)) on thermolysis of the initially formed nonacarbonyl precursors (8 and 9 for R = CH3), which are a mixture of isomers. Direct reaction of 7a with diphenylacetylene at 100 °C gives somewhat lower yields of 11. The reaction of 7b with dimethylacetylenedicarboxylate or the direct reaction of 3 with this alkyne yields the nonacarbonyl derivative Os3(CO)9(μ-η2-C=N(CH2) 3)(μ3-η3-CH3O 2CC=C(H)CO2CH3) (12). Direct reaction of 7a with a 2.5 molar excess trimethylamine N-oxide at room temperature yields the alkyne-imidoyl-coupled product Os3(CO)8(μ-η6-CH 3C(H)=C(CH3)C-(CH3)=C(CH 3)C=N(CH2)3) (13). The solid state structures of 5, 11, 12, and 13 are reported. A comparative study of the electrochemical properties of 5 and 1 is also reported.

UR - https://iris.uniupo.it/handle/11579/32871

U2 - 10.1021/om9610915

DO - 10.1021/om9610915

M3 - Article

SN - 0276-7333

VL - 16

SP - 2674

EP - 2681

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Comparative Reactivity of Triruthenium and Triosmium µ3-h2-Imidoyls, Part 2: Reactions with Alkynes

Abstract

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