Allenylphosphonium complexes of rhodium and iridium

Ian A. Cade; Annie L. Colebatch; Anthony F. Hill; Anthony C. Willis

doi:10.1021/om500450e

Allenylphosphonium complexes of rhodium and iridium

Ian A. Cade, Annie L. Colebatch, Anthony F. Hill^*, Anthony C. Willis

^*Corresponding author for this work

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

3 Citations (Scopus)

Abstract

The propargylic salt [Ph₃PCH₂C≡CH]PF ₆ ([1]PF₆) undergoes a facile rearrangement to the allenyl isomer [Ph₃PCH=C=CH₂]PF₆ ([2]PF₆) upon coordination to rhodium and iridium. The η²- allenylphosphonium salts [IrX(η²-CH₂=C=CHPPh ₃)(CO)(PPh₃)₂]PF₆ (X = Cl, [4]PF₆; X = Br, [5]PF₆) and [RhCl(η²- CH₂=C=CHPPh₃)(PPh₃)₂]PF₆ ([7]PF₆) have been synthesized and characterized, including X-ray crystallographic analyses. In the case of rhodium, it was found that [7]PF ₆ was also formed by the reaction of the α-alkynylphosphonium salt [Ph₃PC≡CCH₃]PF₆ ([3]PF₆) with [RhCl(PPh₃)₃]. The complex [RhCl(CO)(PPh ₃)₂] was found to catalyze the isomerization of [1] ⁺ to [2]⁺.

Original language	English
Pages (from-to)	3198-3204
Number of pages	7
Journal	Organometallics
Volume	33
Issue number	12
DOIs	https://doi.org/10.1021/om500450e
Publication status	Published - 23 Jun 2014

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@article{cf449661d08e423aab1ff400f94f1737,

title = "Allenylphosphonium complexes of rhodium and iridium",

abstract = "The propargylic salt [Ph3PCH2C≡CH]PF 6 ([1]PF6) undergoes a facile rearrangement to the allenyl isomer [Ph3PCH=C=CH2]PF6 ([2]PF6) upon coordination to rhodium and iridium. The η2- allenylphosphonium salts [IrX(η2-CH2=C=CHPPh 3)(CO)(PPh3)2]PF6 (X = Cl, [4]PF6; X = Br, [5]PF6) and [RhCl(η2- CH2=C=CHPPh3)(PPh3)2]PF6 ([7]PF6) have been synthesized and characterized, including X-ray crystallographic analyses. In the case of rhodium, it was found that [7]PF 6 was also formed by the reaction of the α-alkynylphosphonium salt [Ph3PC≡CCH3]PF6 ([3]PF6) with [RhCl(PPh3)3]. The complex [RhCl(CO)(PPh 3)2] was found to catalyze the isomerization of [1] + to [2]+.",

author = "Cade, {Ian A.} and Colebatch, {Annie L.} and Hill, {Anthony F.} and Willis, {Anthony C.}",

year = "2014",

month = jun,

day = "23",

doi = "10.1021/om500450e",

language = "English",

volume = "33",

pages = "3198--3204",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Allenylphosphonium complexes of rhodium and iridium

AU - Cade, Ian A.

AU - Colebatch, Annie L.

AU - Hill, Anthony F.

AU - Willis, Anthony C.

PY - 2014/6/23

Y1 - 2014/6/23

N2 - The propargylic salt [Ph3PCH2C≡CH]PF 6 ([1]PF6) undergoes a facile rearrangement to the allenyl isomer [Ph3PCH=C=CH2]PF6 ([2]PF6) upon coordination to rhodium and iridium. The η2- allenylphosphonium salts [IrX(η2-CH2=C=CHPPh 3)(CO)(PPh3)2]PF6 (X = Cl, [4]PF6; X = Br, [5]PF6) and [RhCl(η2- CH2=C=CHPPh3)(PPh3)2]PF6 ([7]PF6) have been synthesized and characterized, including X-ray crystallographic analyses. In the case of rhodium, it was found that [7]PF 6 was also formed by the reaction of the α-alkynylphosphonium salt [Ph3PC≡CCH3]PF6 ([3]PF6) with [RhCl(PPh3)3]. The complex [RhCl(CO)(PPh 3)2] was found to catalyze the isomerization of [1] + to [2]+.

AB - The propargylic salt [Ph3PCH2C≡CH]PF 6 ([1]PF6) undergoes a facile rearrangement to the allenyl isomer [Ph3PCH=C=CH2]PF6 ([2]PF6) upon coordination to rhodium and iridium. The η2- allenylphosphonium salts [IrX(η2-CH2=C=CHPPh 3)(CO)(PPh3)2]PF6 (X = Cl, [4]PF6; X = Br, [5]PF6) and [RhCl(η2- CH2=C=CHPPh3)(PPh3)2]PF6 ([7]PF6) have been synthesized and characterized, including X-ray crystallographic analyses. In the case of rhodium, it was found that [7]PF 6 was also formed by the reaction of the α-alkynylphosphonium salt [Ph3PC≡CCH3]PF6 ([3]PF6) with [RhCl(PPh3)3]. The complex [RhCl(CO)(PPh 3)2] was found to catalyze the isomerization of [1] + to [2]+.

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U2 - 10.1021/om500450e

DO - 10.1021/om500450e

M3 - Article

SN - 0276-7333

VL - 33

SP - 3198

EP - 3204

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Allenylphosphonium complexes of rhodium and iridium

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