C9DT01071H%3Daccepted%20manuscript.pdf (1.13 MB)
Cyaphide-alkynyl complexes: metal-ligand conjugation and the influence of remote substituents
journal contribution
posted on 2023-06-21, 06:01 authored by Samantha Furfari, Matthew Leech, Nicola Trathen, Madeleine Levis, Ian CrossleyIan CrossleyA homologous series of novel trans-cyaphide-alkynyl complexes, viz. trans-[Ru(dppe)2(C?P)(C?CC6H4R-p)] (R = Me, H, F, CO2Me, NO2) is prepared and comprehensively characterised, alongside their parent phosphaalkyne-complex cations trans-[Ru(dppe)2(?1-P?CSiMe3)(C?CC6H4R-p)]+. Structural data for trans-[Ru(dppe)2(C?P)(C?CC6H4R-p)] (R = Me, F) and trans-[Ru(dppe)2(?1-P?CSiMe3)(C?CC6H4R-p)]+ (R = F, CO2Me) are described, along with that for the previously reported trans-[Ru(dppe)2(C?P)(C?CCO2Me)]. NMR spectroscopic data indicate significant influence of the remote aromatic substituent over the properties of the cyaphide ligand, in line with the Hammett parameter (?p), suggesting appreciable ‘communication’ along the through-conjugate chain. Cyclic voltammety shows irreversible oxidative behaviour, at more anodic Epa than in the respective alkynyl-chloride complexes, though apparently moderated by the remote substituent.
Funding
Linearly Conjugated Phosphacarbon Organometallics; G1810; EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCIL; EP/N016785/1
EPSRC Doctoral Training Partnership 2016-17; G1950; EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCIL; EP/N509784/1
Polymetallaphosphacarbons: Toward phosphorus-doped organometallic molecular wires; G1182; ROYAL SOCIETY; UF120021
Crossley - Conjugate phosphapolyynyls: en route to functional phosphaorganometallic polymers; G0200; LEVERHULME TRUST; F/00 230/AL
History
Publication status
- Published
File Version
- Accepted version
Journal
Dalton TransactionsISSN
1477-9226Publisher
Royal Society of ChemistryExternal DOI
Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2019-04-29First Open Access (FOA) Date
2020-04-24First Compliant Deposit (FCD) Date
2019-04-27Usage metrics
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