Cyaphide-alkynyl complexes: metal-ligand conjugation and the influence of remote substituents

Furfari, Samantha, Leech, Matthew, Trathen, Nicola, Levis, Madeleine Claire and Crossley, Ian (2019) Cyaphide-alkynyl complexes: metal-ligand conjugation and the influence of remote substituents. Dalton Transactions. ISSN 1477-9226

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Abstract

A 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.

Item Type: Article
Keywords: alkynyl, organometallic, cyaphide, phosphorus, nmr, electrochemistry
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry > QD0146 Inorganic chemistry
Q Science > QD Chemistry > QD0241 Organic chemistry > QD0411 Organometallic chemistry and compounds
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Depositing User: Ian Crossley
Date Deposited: 29 Apr 2019 12:57
Last Modified: 01 Jul 2019 15:47
URI: http://sro.sussex.ac.uk/id/eprint/83435

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Project NameSussex Project NumberFunderFunder Ref
Linearly Conjugated Phosphacarbon OrganometallicsG1810EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCILEP/N016785/1
Crossley - Conjugate phosphapolyynyls: en route to functional phosphaorganometallic polymersG0200LEVERHULME TRUSTF/00 230/AL
Polymetallaphosphacarbons: Toward phosphorus-doped organometallic molecular wiresG1182ROYAL SOCIETYUF120021
EPSRC Doctoral Training Partnership 2016-17G1950EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCILEP/N509784/1