Cumulenylidene and acetylide complexes accessed via stannylated acetylenes and butadiynes

Sergey N. Semenov; Olivier Blacque; Thomas Fox; Koushik Venkatesan; Heinz Berke

doi:10.1021/om100702x

Cumulenylidene and acetylide complexes accessed via stannylated acetylenes and butadiynes

Sergey N. Semenov, Olivier Blacque, Thomas Fox, Koushik Venkatesan, Heinz Berke^*

^*Corresponding author for this work

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

5 Citations (Scopus)

Abstract

The tungsten butatrienylidenes [cis-W(CO)(dppe)₂{C=C=C=C(R) (SnMe₃)}] (R = SnMe₃ (2) and SiMe₃ (3); dppe = 1,2-bis(diphenylphosphinoethane)) were prepared from the reactions of [trans-W(CO)(N₂)(dppe)₂] (1) and the respective butadiynes displaying a 1,4-shift of the respective SnMe₃ groups along the butadiyne chains. Stannyl deprotection of 2 with NBu₄F·3H ₂O led to the anionic butadiyne derivative [trans-W(CO)(dppe) ₂(C≡CC≡CH)][NBu₄] (10). The reaction of 1 with stannylated acetylenes gave the vinylidene derivatives [cis-W(CO)(dppe) ₂{C=C(SnMe₃)(R)}] (R = Ph (5) or SnMe₃ (6)), which lost a SnMe₃ group, yielding W(I) acetylides of the type [trans-W(CO)(dppe)₂(C≡CR)] (R = Ph (7), SnMe₃ (8), and SiMe₃ (9)). They were studied by cyclic voltammetry and EPR spectroscopy.

Original language	English
Pages (from-to)	6321-6328
Number of pages	8
Journal	Organometallics
Volume	29
Issue number	23
DOIs	https://doi.org/10.1021/om100702x
Publication status	Published - 13 Dec 2010
Externally published	Yes

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@article{f2a0858c3f484f6380bcb30ac53b9350,

title = "Cumulenylidene and acetylide complexes accessed via stannylated acetylenes and butadiynes",

abstract = "The tungsten butatrienylidenes [cis-W(CO)(dppe)2{C=C=C=C(R) (SnMe3)}] (R = SnMe3 (2) and SiMe3 (3); dppe = 1,2-bis(diphenylphosphinoethane)) were prepared from the reactions of [trans-W(CO)(N2)(dppe)2] (1) and the respective butadiynes displaying a 1,4-shift of the respective SnMe3 groups along the butadiyne chains. Stannyl deprotection of 2 with NBu4F·3H 2O led to the anionic butadiyne derivative [trans-W(CO)(dppe) 2(C≡CC≡CH)][NBu4] (10). The reaction of 1 with stannylated acetylenes gave the vinylidene derivatives [cis-W(CO)(dppe) 2{C=C(SnMe3)(R)}] (R = Ph (5) or SnMe3 (6)), which lost a SnMe3 group, yielding W(I) acetylides of the type [trans-W(CO)(dppe)2(C≡CR)] (R = Ph (7), SnMe3 (8), and SiMe3 (9)). They were studied by cyclic voltammetry and EPR spectroscopy.",

author = "Semenov, {Sergey N.} and Olivier Blacque and Thomas Fox and Koushik Venkatesan and Heinz Berke",

year = "2010",

month = dec,

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doi = "10.1021/om100702x",

language = "English",

volume = "29",

pages = "6321--6328",

journal = "Organometallics",

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T1 - Cumulenylidene and acetylide complexes accessed via stannylated acetylenes and butadiynes

AU - Semenov, Sergey N.

AU - Blacque, Olivier

AU - Fox, Thomas

AU - Venkatesan, Koushik

AU - Berke, Heinz

PY - 2010/12/13

Y1 - 2010/12/13

N2 - The tungsten butatrienylidenes [cis-W(CO)(dppe)2{C=C=C=C(R) (SnMe3)}] (R = SnMe3 (2) and SiMe3 (3); dppe = 1,2-bis(diphenylphosphinoethane)) were prepared from the reactions of [trans-W(CO)(N2)(dppe)2] (1) and the respective butadiynes displaying a 1,4-shift of the respective SnMe3 groups along the butadiyne chains. Stannyl deprotection of 2 with NBu4F·3H 2O led to the anionic butadiyne derivative [trans-W(CO)(dppe) 2(C≡CC≡CH)][NBu4] (10). The reaction of 1 with stannylated acetylenes gave the vinylidene derivatives [cis-W(CO)(dppe) 2{C=C(SnMe3)(R)}] (R = Ph (5) or SnMe3 (6)), which lost a SnMe3 group, yielding W(I) acetylides of the type [trans-W(CO)(dppe)2(C≡CR)] (R = Ph (7), SnMe3 (8), and SiMe3 (9)). They were studied by cyclic voltammetry and EPR spectroscopy.

AB - The tungsten butatrienylidenes [cis-W(CO)(dppe)2{C=C=C=C(R) (SnMe3)}] (R = SnMe3 (2) and SiMe3 (3); dppe = 1,2-bis(diphenylphosphinoethane)) were prepared from the reactions of [trans-W(CO)(N2)(dppe)2] (1) and the respective butadiynes displaying a 1,4-shift of the respective SnMe3 groups along the butadiyne chains. Stannyl deprotection of 2 with NBu4F·3H 2O led to the anionic butadiyne derivative [trans-W(CO)(dppe) 2(C≡CC≡CH)][NBu4] (10). The reaction of 1 with stannylated acetylenes gave the vinylidene derivatives [cis-W(CO)(dppe) 2{C=C(SnMe3)(R)}] (R = Ph (5) or SnMe3 (6)), which lost a SnMe3 group, yielding W(I) acetylides of the type [trans-W(CO)(dppe)2(C≡CR)] (R = Ph (7), SnMe3 (8), and SiMe3 (9)). They were studied by cyclic voltammetry and EPR spectroscopy.

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JO - Organometallics

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SN - 0276-7333

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ER -

Cumulenylidene and acetylide complexes accessed via stannylated acetylenes and butadiynes

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