Synthesis of a Stable Methylidyne Complex

Anthony F. Hill; Jas S. Ward; Yaoyao Xiong

doi:10.1021/acs.organomet.5b00635

Synthesis of a Stable Methylidyne Complex

Anthony F. Hill^*, Jas S. Ward, Yaoyao Xiong

^*Corresponding author for this work

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

21 Citations (Scopus)

Abstract

The successive treatment of [W(CO)₆] with LiSiPh₃, (OCBr)₂, and 4-picoline (pic) affords the silylcarbyne complex [W(≡CSiPh₃)Br(CO)₂(pic)₂], which reacts with 1,2-bis(dicyclohexylphoshino)ethane (dcpe), 1,2-bis(diphenylphosphino)ethane (dppe), and tetramethylethylenediamine (tmeda) to provide the complexes [W(≡CSiPh₃)Br(CO)₂(L₂)] (L₂ = dcpe, dppe, tmeda). Fluoride-mediated protodesilylation of [W(≡CSiPh₃)Br(CO)₂(dcpe)] with moist [Bu₄N]F provides the stable and structurally characterized terminal methylidyne complex [W(≡CH)Br(CO)₂(dcpe)] (shown) in addition to traces of the ethene-1,2-diylidyne complex {Br(dcpe)(CO)₂W}₂(μ-≡CCH=CHC≡).

Original language	English
Pages (from-to)	5057-5064
Number of pages	8
Journal	Organometallics
Volume	34
Issue number	20
DOIs	https://doi.org/10.1021/acs.organomet.5b00635
Publication status	Published - 26 Oct 2015

Access to Document

10.1021/acs.organomet.5b00635

Cite this

@article{6caff021362e421ebdb4aa33bd58d7c6,

title = "Synthesis of a Stable Methylidyne Complex",

abstract = "The successive treatment of [W(CO)6] with LiSiPh3, (OCBr)2, and 4-picoline (pic) affords the silylcarbyne complex [W(≡CSiPh3)Br(CO)2(pic)2], which reacts with 1,2-bis(dicyclohexylphoshino)ethane (dcpe), 1,2-bis(diphenylphosphino)ethane (dppe), and tetramethylethylenediamine (tmeda) to provide the complexes [W(≡CSiPh3)Br(CO)2(L2)] (L2 = dcpe, dppe, tmeda). Fluoride-mediated protodesilylation of [W(≡CSiPh3)Br(CO)2(dcpe)] with moist [Bu4N]F provides the stable and structurally characterized terminal methylidyne complex [W(≡CH)Br(CO)2(dcpe)] (shown) in addition to traces of the ethene-1,2-diylidyne complex \{Br(dcpe)(CO)2W\}2(μ-≡CCH=CHC≡).",

author = "Hill, \{Anthony F.\} and Ward, \{Jas S.\} and Yaoyao Xiong",

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

year = "2015",

month = oct,

day = "26",

doi = "10.1021/acs.organomet.5b00635",

language = "English",

volume = "34",

pages = "5057--5064",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "20",

}

TY - JOUR

T1 - Synthesis of a Stable Methylidyne Complex

AU - Hill, Anthony F.

AU - Ward, Jas S.

AU - Xiong, Yaoyao

PY - 2015/10/26

Y1 - 2015/10/26

N2 - The successive treatment of [W(CO)6] with LiSiPh3, (OCBr)2, and 4-picoline (pic) affords the silylcarbyne complex [W(≡CSiPh3)Br(CO)2(pic)2], which reacts with 1,2-bis(dicyclohexylphoshino)ethane (dcpe), 1,2-bis(diphenylphosphino)ethane (dppe), and tetramethylethylenediamine (tmeda) to provide the complexes [W(≡CSiPh3)Br(CO)2(L2)] (L2 = dcpe, dppe, tmeda). Fluoride-mediated protodesilylation of [W(≡CSiPh3)Br(CO)2(dcpe)] with moist [Bu4N]F provides the stable and structurally characterized terminal methylidyne complex [W(≡CH)Br(CO)2(dcpe)] (shown) in addition to traces of the ethene-1,2-diylidyne complex {Br(dcpe)(CO)2W}2(μ-≡CCH=CHC≡).

AB - The successive treatment of [W(CO)6] with LiSiPh3, (OCBr)2, and 4-picoline (pic) affords the silylcarbyne complex [W(≡CSiPh3)Br(CO)2(pic)2], which reacts with 1,2-bis(dicyclohexylphoshino)ethane (dcpe), 1,2-bis(diphenylphosphino)ethane (dppe), and tetramethylethylenediamine (tmeda) to provide the complexes [W(≡CSiPh3)Br(CO)2(L2)] (L2 = dcpe, dppe, tmeda). Fluoride-mediated protodesilylation of [W(≡CSiPh3)Br(CO)2(dcpe)] with moist [Bu4N]F provides the stable and structurally characterized terminal methylidyne complex [W(≡CH)Br(CO)2(dcpe)] (shown) in addition to traces of the ethene-1,2-diylidyne complex {Br(dcpe)(CO)2W}2(μ-≡CCH=CHC≡).

UR - https://www.scopus.com/pages/publications/84945947295

U2 - 10.1021/acs.organomet.5b00635

DO - 10.1021/acs.organomet.5b00635

M3 - Article

SN - 0276-7333

VL - 34

SP - 5057

EP - 5064

JO - Organometallics

JF - Organometallics

IS - 20

ER -

Synthesis of a Stable Methylidyne Complex

Abstract

Access to Document

Other files and links

Fingerprint

Cite this