η2-allenyl- and η2-alkynylphosphonium complexes of platinum

Annie L. Colebatch; Ian A. Cade; Anthony F. Hill; Mohan M. Bhadbhade

doi:10.1021/om400406s

η²-allenyl- and η²-alkynylphosphonium complexes of platinum

Annie L. Colebatch, Ian A. Cade, Anthony F. Hill^*, Mohan M. Bhadbhade

^*Corresponding author for this work

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

10 Citations (Scopus)

Abstract

The reaction of the propargylic salt [Ph₃PCH₂Cî - CH]PF₆ with [Pt(C₂H₄)(PPh₃) ₂] affords the η²-allenylphosphonium salt [Pt(η²-CH₂î - "Cî - "CHPPh ₃)(PPh₃)₂]PF₆ via a metal-mediated propargylic rearrangement. Isomerization of the complex occurs in solution to generate the salt [Pt{η²-C(PPh₃)î - "Cî - "CH₂}(PPh₃)₂]PF ₆, wherein the allene is coordinated by the internal Cî - "C bond. Computational studies indicate that the isomerization of the propargylic cation [Ph₃PCH₂Cî - CH]⁺ to the allenyl species [Ph₃PCHî - "Cî - "CH ₂]⁺ and the α-alkynyl isomer [Ph ₃PCî - CCH₃]⁺ is thermodynamically favorable. The isomeric η²-alkynylphosphonium salt [Ptη²-C(CH₃)î - CPPh₃(PPh ₃)₂]PF₆ is formed from the reaction of [Ph ₃PCî - CCH₃]PF₆ with [Pt(C ₂H₄)(PPh₃)₂] and does not isomerize to the propargylic or allenyl forms.

Original language	English
Pages (from-to)	4766-4774
Number of pages	9
Journal	Organometallics
Volume	32
Issue number	17
DOIs	https://doi.org/10.1021/om400406s
Publication status	Published - 9 Sept 2013

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@article{a404469de75945ba924c28d9201605aa,

title = "η2-allenyl- and η2-alkynylphosphonium complexes of platinum",

abstract = "The reaction of the propargylic salt [Ph3PCH2C{\^i} - CH]PF6 with [Pt(C2H4)(PPh3) 2] affords the η2-allenylphosphonium salt [Pt(η2-CH2{\^i} - {"}C{\^i} - {"}CHPPh 3)(PPh3)2]PF6 via a metal-mediated propargylic rearrangement. Isomerization of the complex occurs in solution to generate the salt [Pt{η2-C(PPh3){\^i} - {"}C{\^i} - {"}CH2}(PPh3)2]PF 6, wherein the allene is coordinated by the internal C{\^i} - {"}C bond. Computational studies indicate that the isomerization of the propargylic cation [Ph3PCH2C{\^i} - CH]+ to the allenyl species [Ph3PCH{\^i} - {"}C{\^i} - {"}CH 2]+ and the α-alkynyl isomer [Ph 3PC{\^i} - CCH3]+ is thermodynamically favorable. The isomeric η2-alkynylphosphonium salt [Ptη2-C(CH3){\^i} - CPPh3(PPh 3)2]PF6 is formed from the reaction of [Ph 3PC{\^i} - CCH3]PF6 with [Pt(C 2H4)(PPh3)2] and does not isomerize to the propargylic or allenyl forms.",

author = "Colebatch, {Annie L.} and Cade, {Ian A.} and Hill, {Anthony F.} and Bhadbhade, {Mohan M.}",

year = "2013",

month = sep,

day = "9",

doi = "10.1021/om400406s",

language = "English",

volume = "32",

pages = "4766--4774",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "17",

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T1 - η2-allenyl- and η2-alkynylphosphonium complexes of platinum

AU - Colebatch, Annie L.

AU - Cade, Ian A.

AU - Hill, Anthony F.

AU - Bhadbhade, Mohan M.

PY - 2013/9/9

Y1 - 2013/9/9

N2 - The reaction of the propargylic salt [Ph3PCH2Cî - CH]PF6 with [Pt(C2H4)(PPh3) 2] affords the η2-allenylphosphonium salt [Pt(η2-CH2î - "Cî - "CHPPh 3)(PPh3)2]PF6 via a metal-mediated propargylic rearrangement. Isomerization of the complex occurs in solution to generate the salt [Pt{η2-C(PPh3)î - "Cî - "CH2}(PPh3)2]PF 6, wherein the allene is coordinated by the internal Cî - "C bond. Computational studies indicate that the isomerization of the propargylic cation [Ph3PCH2Cî - CH]+ to the allenyl species [Ph3PCHî - "Cî - "CH 2]+ and the α-alkynyl isomer [Ph 3PCî - CCH3]+ is thermodynamically favorable. The isomeric η2-alkynylphosphonium salt [Ptη2-C(CH3)î - CPPh3(PPh 3)2]PF6 is formed from the reaction of [Ph 3PCî - CCH3]PF6 with [Pt(C 2H4)(PPh3)2] and does not isomerize to the propargylic or allenyl forms.

AB - The reaction of the propargylic salt [Ph3PCH2Cî - CH]PF6 with [Pt(C2H4)(PPh3) 2] affords the η2-allenylphosphonium salt [Pt(η2-CH2î - "Cî - "CHPPh 3)(PPh3)2]PF6 via a metal-mediated propargylic rearrangement. Isomerization of the complex occurs in solution to generate the salt [Pt{η2-C(PPh3)î - "Cî - "CH2}(PPh3)2]PF 6, wherein the allene is coordinated by the internal Cî - "C bond. Computational studies indicate that the isomerization of the propargylic cation [Ph3PCH2Cî - CH]+ to the allenyl species [Ph3PCHî - "Cî - "CH 2]+ and the α-alkynyl isomer [Ph 3PCî - CCH3]+ is thermodynamically favorable. The isomeric η2-alkynylphosphonium salt [Ptη2-C(CH3)î - CPPh3(PPh 3)2]PF6 is formed from the reaction of [Ph 3PCî - CCH3]PF6 with [Pt(C 2H4)(PPh3)2] and does not isomerize to the propargylic or allenyl forms.

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U2 - 10.1021/om400406s

DO - 10.1021/om400406s

M3 - Article

SN - 0276-7333

VL - 32

SP - 4766

EP - 4774

JO - Organometallics

JF - Organometallics

IS - 17

ER -

η²-allenyl- and η²-alkynylphosphonium complexes of platinum

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