Skip navigation
Skip navigation

In Search of Fulminate Analogues: Ln M≡CP=NR

Frogley, Benjamin; Hill, Anthony; Shang, Rong; Sharma, Manab; Willis, Anthony

Description

The "CPNR" ligand may be viewed as being isolobal with fulminate, CNO; however, attempts to prepare a complex of such a ligand resulted instead in a range of novel imino and aminophosphinocarbyne complexes. Sequential treatment of [Mo(≡CBr)(CO)2 (Tp*)] (Tp*=hydrotris(dimethylpyrazolyl)borate) with nBuLi and ClP=NMes* (Mes*=C6 H2 tBu3 -2,4,6) afforded mixtures of the complexes [Mo(≡CPnBuNHMes*)(CO)2 (Tp*)] and traces of the bimetallic products [Mo2 {μ2 -C2 P2 O(NHMes)2 }(CO)4 (Tp*)2 ] and [Mo2...[Show more]

dc.contributor.authorFrogley, Benjamin
dc.contributor.authorHill, Anthony
dc.contributor.authorShang, Rong
dc.contributor.authorSharma, Manab
dc.contributor.authorWillis, Anthony
dc.date.accessioned2020-12-13T23:41:50Z
dc.identifier.issn0947-6539
dc.identifier.urihttp://hdl.handle.net/1885/217022
dc.description.abstractThe "CPNR" ligand may be viewed as being isolobal with fulminate, CNO; however, attempts to prepare a complex of such a ligand resulted instead in a range of novel imino and aminophosphinocarbyne complexes. Sequential treatment of [Mo(≡CBr)(CO)2 (Tp*)] (Tp*=hydrotris(dimethylpyrazolyl)borate) with nBuLi and ClP=NMes* (Mes*=C6 H2 tBu3 -2,4,6) afforded mixtures of the complexes [Mo(≡CPnBuNHMes*)(CO)2 (Tp*)] and traces of the bimetallic products [Mo2 {μ2 -C2 P2 O(NHMes)2 }(CO)4 (Tp*)2 ] and [Mo2 (μ2 -C2 PNHMes)(CO)4 (Tp*)2 ]. The reaction of [W(≡CBr)(CO)2 (Tp*)] with nBuLi and ClP=NMes* afforded predominantly the mononuclear carbyne [W{≡CP(=NMes*)nBu2 })(CO)2 (Tp*)] and traces of the binuclear complex [W2 (μ-C2 PNHMes)(CO)4 (Tp*)2 ] which is also obtained when tBuLi is used. Although not isolable, the intended complexes [M(≡CPNMes*)(CO)2 (Tp*)] could be generated in situ and spectroscopically characterized via the reactions of the stannyl carbynes [M(≡CSnnBu3 )(CO)2 (Tp*)] and ClP=NMes*. The preceding observations are mechanistically interpreted with reference to a computational interrogation of the model complex [Mo(≡CP=NCH3 )(CO)2 (Tp*)], the LUMO of which has considerable phosphorus character.
dc.description.sponsorshipWe gratefully acknowledge the Australian Research Council(DP170102695 and DP190100723) for funding.
dc.format.mimetypeapplication/pdf
dc.language.isoen_AU
dc.publisherWiley
dc.rights© 2020 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
dc.sourceChemistry - A European Journal
dc.subjectalkylidyne
dc.subjectbinuclear
dc.subjectcarbyne
dc.subjectfulminate
dc.subjectiminophosphane
dc.titleIn Search of Fulminate Analogues: Ln M≡CP=NR
dc.typeJournal article
local.identifier.citationvolume26
dc.date.issued2020-07-17
local.publisher.urlhttps://www.wiley.com/en-gb
local.type.statusAccepted Version
local.contributor.affiliationFrogley, B., Research School of Chemistry,The Australian National University
local.contributor.affiliationHill, A., Research School of Chemistry,The Australian National University
local.contributor.affiliationSharma, M., Research School of Chemistry,The Australian National University
local.contributor.affiliationWillis, A., Research School of Chemistry,The Australian National University
local.description.embargo2021-07-17
dc.relationhttp://purl.org/au-research/grants/arc/DP170102695
dc.relationhttp://purl.org/au-research/grants/arc/DP190100723
local.identifier.essn1521-3765
local.bibliographicCitation.issue40
local.bibliographicCitation.startpage8819
local.bibliographicCitation.lastpage8827
local.identifier.doi10.1002/chem.202000635
dcterms.accessRightsOpen Access
dc.provenancehttps://v2.sherpa.ac.uk/id/publication/1518......"The Accepted Version can be archived in a Non-Commercial Repository. 12 months embargo" from SHERPA/RoMEO site (as at 14/12/2020). This is the peer reviewed version of the following article: [Frogley, Benjamin J., et al. "In Search of Fulminate Analogues: L n M≡ CP= NR." Chemistry (Weinheim an der Bergstrasse, Germany) 26.40 (2020): 8819-8827.], which has been published in final form at https://dx.doi.org/10.1002/chem.202000635. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
CollectionsANU Research Publications

Download

File Description SizeFormat Image
10.1002_chem_202000635.pdf2.26 MBAdobe PDFThumbnail


Items in Open Research are protected by copyright, with all rights reserved, unless otherwise indicated.

Updated:  19 May 2020/ Responsible Officer:  University Librarian/ Page Contact:  Library Systems & Web Coordinator