Synthesis of phosphonium-substituted vinylidene complexes from [HC≡CCH2PPh3]+: Exploring the Competition between Allene and Vinylidene Formation.

Elizabeth J. Smith; Natalie E. Pridmore; Adrian C. Whitwood; Jason M. Lynam

doi:10.1021/om5010429

Synthesis of phosphonium-substituted vinylidene complexes from [HC≡CCH₂PPh₃]⁺: Exploring the Competition between Allene and Vinylidene Formation.

Elizabeth J. Smith, Natalie E. Pridmore, Adrian C. Whitwood, Jason M. Lynam^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

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Abstract

Reaction of the alkenyl-substituted carbene complex [Ru(κ²-O₂CMe)(OC{Me}O(=CCH=CH₂)(PPh₃)₂]⁺ with PPh₃ results in the formation of the vinylidene-containing species [Ru(κ¹-O₂CMe)(κ²-O₂CMe)(=C=CHCH₂PPh₃)(PPh₃)₂]⁺, among other products. This complex could also be obtained by reaction of [Ru(κ²-O₂CR)(PPh₃)₂] (R = Me, Ph) with [HC≡CCH₂PPh₃]⁺ although in this instance competitive formation of allene-containing [Ru(κ¹-O₂CR)(κ²-O₂CR)(η²-H₂C=C=CHPPh₃)(PPh₃)₂] occurred. Reaction of [Ru(κ²-O₂CMe)₂(PPh₃)₂] with [H₂C=C=CHPPh₃]⁺ gives this allene complex in a selective fashion. Similar results were obtained when [RhCl(PⁱPr₃)₂]₂ was used as the metal precursor. The reaction with [H₂C=C=CHPPh₃]⁺ gave [RhCl(η²-H₂C=C=CHPPh₃)(PⁱPr₃)₂]⁺, whereas treatment with [HC≡CCH₂PPh₃]⁺ afforded a mixture of the same complex and [RhCl(η²-HC≡CCH₂PPh₃)(PⁱPr₃)₂]⁺, which subsequently isomerized to vinylidene-containing [RhCl(=C=CHCH₂PPh₃)(PⁱPr₃)₂]⁺ via the alkynyl hydride complex [RhCl(H)(C≡CCH₂PPh₃)(PⁱPr₃)₂]⁺. Consistent with previous findings [HC≡CCH₂PPh₃]⁺ isomerizes to [H₂C=C=CHPPh₃]⁺ in the absence of a metal and the balance between the vinylidene and allene complexes formed in these reactions appears to relate to the efficiency of the reaction with each substrate.

Original language	English
Pages (from-to)	7260-7269
Number of pages	10
Journal	Organometallics
Volume	33
Issue number	24
DOIs	https://doi.org/10.1021/om5010429
Publication status	Published - 22 Dec 2014

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@article{ee345bfa273f47e8a054a2425249a089,

title = "Synthesis of phosphonium-substituted vinylidene complexes from [HC≡CCH2PPh3]+: Exploring the Competition between Allene and Vinylidene Formation.",

abstract = "Reaction of the alkenyl-substituted carbene complex [Ru(κ2-O2CMe)(OC{Me}O(=CCH=CH2)(PPh3)2]+ with PPh3 results in the formation of the vinylidene-containing species [Ru(κ1-O2CMe)(κ2-O2CMe)(=C=CHCH2PPh3)(PPh3)2]+, among other products. This complex could also be obtained by reaction of [Ru(κ2-O2CR)(PPh3)2] (R = Me, Ph) with [HC≡CCH2PPh3]+ although in this instance competitive formation of allene-containing [Ru(κ1-O2CR)(κ2-O2CR)(η2-H2C=C=CHPPh3)(PPh3)2] occurred. Reaction of [Ru(κ2-O2CMe)2(PPh3)2] with [H2C=C=CHPPh3]+ gives this allene complex in a selective fashion. Similar results were obtained when [RhCl(PiPr3)2]2 was used as the metal precursor. The reaction with [H2C=C=CHPPh3]+ gave [RhCl(η2-H2C=C=CHPPh3)(PiPr3)2]+, whereas treatment with [HC≡CCH2PPh3]+ afforded a mixture of the same complex and [RhCl(η2-HC≡CCH2PPh3)(PiPr3)2]+, which subsequently isomerized to vinylidene-containing [RhCl(=C=CHCH2PPh3)(PiPr3)2]+ via the alkynyl hydride complex [RhCl(H)(C≡CCH2PPh3)(PiPr3)2]+. Consistent with previous findings [HC≡CCH2PPh3]+ isomerizes to [H2C=C=CHPPh3]+ in the absence of a metal and the balance between the vinylidene and allene complexes formed in these reactions appears to relate to the efficiency of the reaction with each substrate.",

author = "Smith, {Elizabeth J.} and Pridmore, {Natalie E.} and Whitwood, {Adrian C.} and Lynam, {Jason M.}",

year = "2014",

month = dec,

day = "22",

doi = "10.1021/om5010429",

language = "English",

volume = "33",

pages = "7260--7269",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "24",

}

Synthesis of phosphonium-substituted vinylidene complexes from [HC≡CCH₂PPh₃]⁺: Exploring the Competition between Allene and Vinylidene Formation. / Smith, Elizabeth J.; Pridmore, Natalie E.; Whitwood, Adrian C. et al.
In: Organometallics, Vol. 33, No. 24, 22.12.2014, p. 7260-7269.

Research output: Contribution to journal › Article (Academic Journal) › peer-review

TY - JOUR

T1 - Synthesis of phosphonium-substituted vinylidene complexes from [HC≡CCH2PPh3]+

T2 - Exploring the Competition between Allene and Vinylidene Formation.

AU - Smith, Elizabeth J.

AU - Pridmore, Natalie E.

AU - Whitwood, Adrian C.

AU - Lynam, Jason M.

PY - 2014/12/22

Y1 - 2014/12/22

N2 - Reaction of the alkenyl-substituted carbene complex [Ru(κ2-O2CMe)(OC{Me}O(=CCH=CH2)(PPh3)2]+ with PPh3 results in the formation of the vinylidene-containing species [Ru(κ1-O2CMe)(κ2-O2CMe)(=C=CHCH2PPh3)(PPh3)2]+, among other products. This complex could also be obtained by reaction of [Ru(κ2-O2CR)(PPh3)2] (R = Me, Ph) with [HC≡CCH2PPh3]+ although in this instance competitive formation of allene-containing [Ru(κ1-O2CR)(κ2-O2CR)(η2-H2C=C=CHPPh3)(PPh3)2] occurred. Reaction of [Ru(κ2-O2CMe)2(PPh3)2] with [H2C=C=CHPPh3]+ gives this allene complex in a selective fashion. Similar results were obtained when [RhCl(PiPr3)2]2 was used as the metal precursor. The reaction with [H2C=C=CHPPh3]+ gave [RhCl(η2-H2C=C=CHPPh3)(PiPr3)2]+, whereas treatment with [HC≡CCH2PPh3]+ afforded a mixture of the same complex and [RhCl(η2-HC≡CCH2PPh3)(PiPr3)2]+, which subsequently isomerized to vinylidene-containing [RhCl(=C=CHCH2PPh3)(PiPr3)2]+ via the alkynyl hydride complex [RhCl(H)(C≡CCH2PPh3)(PiPr3)2]+. Consistent with previous findings [HC≡CCH2PPh3]+ isomerizes to [H2C=C=CHPPh3]+ in the absence of a metal and the balance between the vinylidene and allene complexes formed in these reactions appears to relate to the efficiency of the reaction with each substrate.

AB - Reaction of the alkenyl-substituted carbene complex [Ru(κ2-O2CMe)(OC{Me}O(=CCH=CH2)(PPh3)2]+ with PPh3 results in the formation of the vinylidene-containing species [Ru(κ1-O2CMe)(κ2-O2CMe)(=C=CHCH2PPh3)(PPh3)2]+, among other products. This complex could also be obtained by reaction of [Ru(κ2-O2CR)(PPh3)2] (R = Me, Ph) with [HC≡CCH2PPh3]+ although in this instance competitive formation of allene-containing [Ru(κ1-O2CR)(κ2-O2CR)(η2-H2C=C=CHPPh3)(PPh3)2] occurred. Reaction of [Ru(κ2-O2CMe)2(PPh3)2] with [H2C=C=CHPPh3]+ gives this allene complex in a selective fashion. Similar results were obtained when [RhCl(PiPr3)2]2 was used as the metal precursor. The reaction with [H2C=C=CHPPh3]+ gave [RhCl(η2-H2C=C=CHPPh3)(PiPr3)2]+, whereas treatment with [HC≡CCH2PPh3]+ afforded a mixture of the same complex and [RhCl(η2-HC≡CCH2PPh3)(PiPr3)2]+, which subsequently isomerized to vinylidene-containing [RhCl(=C=CHCH2PPh3)(PiPr3)2]+ via the alkynyl hydride complex [RhCl(H)(C≡CCH2PPh3)(PiPr3)2]+. Consistent with previous findings [HC≡CCH2PPh3]+ isomerizes to [H2C=C=CHPPh3]+ in the absence of a metal and the balance between the vinylidene and allene complexes formed in these reactions appears to relate to the efficiency of the reaction with each substrate.

UR - http://www.scopus.com/inward/record.url?scp=84919725353&partnerID=8YFLogxK

U2 - 10.1021/om5010429

DO - 10.1021/om5010429

M3 - Article (Academic Journal)

AN - SCOPUS:84919725353

SN - 0276-7333

VL - 33

SP - 7260

EP - 7269

JO - Organometallics

JF - Organometallics

IS - 24

ER -

Synthesis of phosphonium-substituted vinylidene complexes from [HC≡CCH₂PPh₃]⁺: Exploring the Competition between Allene and Vinylidene Formation.

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