Redox Reactions of a Stable Dialkylphosphinyl Radical

Fumiya Hirakawa; Hitomi Ichikawa; Shintaro Ishida; Takeaki Iwamoto

doi:10.1021/acs.organomet.5b00323

Redox Reactions of a Stable Dialkylphosphinyl Radical

Fumiya Hirakawa, Hitomi Ichikawa, Shintaro Ishida, Takeaki Iwamoto

SCI - Chemistry

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

15 Citations (Scopus)

Abstract

A stable dialkylphosphinyl radical, 2,2,5,5-tatrakis(trimethylsilyl)-1-phosphacyclopentan-1-yl (R^H₂P^•), showed both irreversible one-electron oxidation and reduction peaks at -0.24 and -2.29 V vs ferrocene/ferrocenium couple. One-electron reduction of R^H₂P^• with KC₈ in the presence of 18-crown-6 (18-c-6) or [2.2.2]cryptand (crypt-222) gave the corresponding phosphides [K(18-c-6)]⁺[R^H₂P]^- and [K(crypt-222)]⁺[R^H₂P]^-. Whereas [K(18-c-6)]⁺[R^H₂P]^- exists as a contact ion pair, [K(crypt-222)]⁺[R^H₂P]^- exists as a solvent-separated ion pair in the solid state. Reaction of R^H₂P^• with AgOTf afforded an unexpected product, a silver(I) phosphaalkene complex. (Chemical Equation Presented).

Original language	English
Pages (from-to)	2714-2716
Number of pages	3
Journal	Organometallics
Volume	34
Issue number	12
DOIs	https://doi.org/10.1021/acs.organomet.5b00323
Publication status	Published - 2015 Jun 22

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

Access to Document

10.1021/acs.organomet.5b00323

Cite this

@article{3647ed9e36324dd7aea6e1476a6350bc,

title = "Redox Reactions of a Stable Dialkylphosphinyl Radical",

abstract = "A stable dialkylphosphinyl radical, 2,2,5,5-tatrakis(trimethylsilyl)-1-phosphacyclopentan-1-yl (RH2P•), showed both irreversible one-electron oxidation and reduction peaks at -0.24 and -2.29 V vs ferrocene/ferrocenium couple. One-electron reduction of RH2P• with KC8 in the presence of 18-crown-6 (18-c-6) or [2.2.2]cryptand (crypt-222) gave the corresponding phosphides [K(18-c-6)]+[RH2P]- and [K(crypt-222)]+[RH2P]-. Whereas [K(18-c-6)]+[RH2P]- exists as a contact ion pair, [K(crypt-222)]+[RH2P]- exists as a solvent-separated ion pair in the solid state. Reaction of RH2P• with AgOTf afforded an unexpected product, a silver(I) phosphaalkene complex. (Chemical Equation Presented).",

author = "Fumiya Hirakawa and Hitomi Ichikawa and Shintaro Ishida and Takeaki Iwamoto",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

month = jun,

day = "22",

doi = "10.1021/acs.organomet.5b00323",

language = "English",

volume = "34",

pages = "2714--2716",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Redox Reactions of a Stable Dialkylphosphinyl Radical

AU - Hirakawa, Fumiya

AU - Ichikawa, Hitomi

AU - Ishida, Shintaro

AU - Iwamoto, Takeaki

PY - 2015/6/22

Y1 - 2015/6/22

N2 - A stable dialkylphosphinyl radical, 2,2,5,5-tatrakis(trimethylsilyl)-1-phosphacyclopentan-1-yl (RH2P•), showed both irreversible one-electron oxidation and reduction peaks at -0.24 and -2.29 V vs ferrocene/ferrocenium couple. One-electron reduction of RH2P• with KC8 in the presence of 18-crown-6 (18-c-6) or [2.2.2]cryptand (crypt-222) gave the corresponding phosphides [K(18-c-6)]+[RH2P]- and [K(crypt-222)]+[RH2P]-. Whereas [K(18-c-6)]+[RH2P]- exists as a contact ion pair, [K(crypt-222)]+[RH2P]- exists as a solvent-separated ion pair in the solid state. Reaction of RH2P• with AgOTf afforded an unexpected product, a silver(I) phosphaalkene complex. (Chemical Equation Presented).

AB - A stable dialkylphosphinyl radical, 2,2,5,5-tatrakis(trimethylsilyl)-1-phosphacyclopentan-1-yl (RH2P•), showed both irreversible one-electron oxidation and reduction peaks at -0.24 and -2.29 V vs ferrocene/ferrocenium couple. One-electron reduction of RH2P• with KC8 in the presence of 18-crown-6 (18-c-6) or [2.2.2]cryptand (crypt-222) gave the corresponding phosphides [K(18-c-6)]+[RH2P]- and [K(crypt-222)]+[RH2P]-. Whereas [K(18-c-6)]+[RH2P]- exists as a contact ion pair, [K(crypt-222)]+[RH2P]- exists as a solvent-separated ion pair in the solid state. Reaction of RH2P• with AgOTf afforded an unexpected product, a silver(I) phosphaalkene complex. (Chemical Equation Presented).

UR - http://www.scopus.com/inward/record.url?scp=84934952609&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84934952609&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.5b00323

DO - 10.1021/acs.organomet.5b00323

M3 - Article

AN - SCOPUS:84934952609

SN - 0276-7333

VL - 34

SP - 2714

EP - 2716

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Redox Reactions of a Stable Dialkylphosphinyl Radical

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this