Stable cyclopropenylvinyl ligands via insertion into a transient cyclopropenyl metal bond

Lachlan J. Watson; Anthony F. Hill

doi:10.1039/d3dt03997h

Stable cyclopropenylvinyl ligands via insertion into a transient cyclopropenyl metal bond

Lachlan J. Watson, Anthony F. Hill^*

^*Corresponding author for this work

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

Abstract

Treatment of the rhodium pincer complexes [RhCl(RPm)] (RPm = N,N '-bis(di-R-phosphinomethyl)perimidinylidene, R = Ph, Cy) with triphenylcyclopropenium hexafluorophosphate affords rhodacyclobutadiene complexes. These in turn react with activated alkynes (RC≡CCO2Me, R = H, CO2Me) to afford unusually stable cyclopropenylvinyls, implicating the intermediacy of sigma-cyclopropenyl isomers. In contrast, treatment of [RhCl{py(NHPtBu2)2-2,6}] with the same reagent instead results in double functionalisation (S_EAr) at the pincer backbone.

Original language	English
Pages (from-to)	3629-3637
Number of pages	9
Journal	Dalton Transactions
Volume	53
Issue number	8
Early online date	16 Jan 2024
DOIs	https://doi.org/10.1039/d3dt03997h
Publication status	Published - 28 Feb 2024

Access to Document

10.1039/d3dt03997h

Cite this

@article{5aaa2bd4029246f2b8c3878f401d2f50,

title = "Stable cyclopropenylvinyl ligands via insertion into a transient cyclopropenyl metal bond",

abstract = "Treatment of the rhodium pincer complexes [RhCl(RPm)] (RPm = N,N '-bis(di-R-phosphinomethyl)perimidinylidene, R = Ph, Cy) with triphenylcyclopropenium hexafluorophosphate affords rhodacyclobutadiene complexes. These in turn react with activated alkynes (RC≡CCO2Me, R = H, CO2Me) to afford unusually stable cyclopropenylvinyls, implicating the intermediacy of sigma-cyclopropenyl isomers. In contrast, treatment of [RhCl\{py(NHPtBu2)2-2,6\}] with the same reagent instead results in double functionalisation (SEAr) at the pincer backbone.",

keywords = "Effective core potentials, C-h, Alkylidyne complexes, Oxidative addition, Structural-characterization, Molecular calculations, Basis-sets, Metathesis, Acetylenes, Eta-3-cyclopropenyl",

author = "Watson, \{Lachlan J.\} and Hill, \{Anthony F.\}",

note = "Publisher Copyright: {\textcopyright} 2024 The Royal Society of Chemistry.",

year = "2024",

month = feb,

day = "28",

doi = "10.1039/d3dt03997h",

language = "English",

volume = "53",

pages = "3629--3637",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "8",

}

TY - JOUR

T1 - Stable cyclopropenylvinyl ligands via insertion into a transient cyclopropenyl metal bond

AU - Watson, Lachlan J.

AU - Hill, Anthony F.

PY - 2024/2/28

Y1 - 2024/2/28

N2 - Treatment of the rhodium pincer complexes [RhCl(RPm)] (RPm = N,N '-bis(di-R-phosphinomethyl)perimidinylidene, R = Ph, Cy) with triphenylcyclopropenium hexafluorophosphate affords rhodacyclobutadiene complexes. These in turn react with activated alkynes (RC≡CCO2Me, R = H, CO2Me) to afford unusually stable cyclopropenylvinyls, implicating the intermediacy of sigma-cyclopropenyl isomers. In contrast, treatment of [RhCl{py(NHPtBu2)2-2,6}] with the same reagent instead results in double functionalisation (SEAr) at the pincer backbone.

AB - Treatment of the rhodium pincer complexes [RhCl(RPm)] (RPm = N,N '-bis(di-R-phosphinomethyl)perimidinylidene, R = Ph, Cy) with triphenylcyclopropenium hexafluorophosphate affords rhodacyclobutadiene complexes. These in turn react with activated alkynes (RC≡CCO2Me, R = H, CO2Me) to afford unusually stable cyclopropenylvinyls, implicating the intermediacy of sigma-cyclopropenyl isomers. In contrast, treatment of [RhCl{py(NHPtBu2)2-2,6}] with the same reagent instead results in double functionalisation (SEAr) at the pincer backbone.

KW - Effective core potentials

KW - C-h

KW - Alkylidyne complexes

KW - Oxidative addition

KW - Structural-characterization

KW - Molecular calculations

KW - Basis-sets

KW - Metathesis

KW - Acetylenes

KW - Eta-3-cyclopropenyl

UR - https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=anu_research_portal_plus2&SrcAuth=WosAPI&KeyUT=WOS:001153947300001&DestLinkType=FullRecord&DestApp=WOS_CPL

UR - https://www.scopus.com/pages/publications/85183958906

U2 - 10.1039/d3dt03997h

DO - 10.1039/d3dt03997h

M3 - Article

C2 - 38289268

SN - 1477-9226

VL - 53

SP - 3629

EP - 3637

JO - Dalton Transactions

JF - Dalton Transactions

IS - 8

ER -

Stable cyclopropenylvinyl ligands via insertion into a transient cyclopropenyl metal bond

Abstract

Access to Document

Other files and links

Fingerprint

Cite this