Controlled reactivity of terminal cyaphide complexes: Isola-tion of the 5-coordinate [Ru(dppe)2(CP)]+

Levis, Madeleine C, Pearce, Kyle G and Crossley, Ian R (2019) Controlled reactivity of terminal cyaphide complexes: Isola-tion of the 5-coordinate [Ru(dppe)2(CP)]+. Inorganic Chemistry. ISSN 0020-1669

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Abstract

The novel cyaphide complex trans-[Ru(dppe)2Me(CP)] is obtained in excellent yields and exhibits the first instance of con-trolled reactivity of any terminal-cyaphide complex. Its treatment with ZnX2 / PPh3 effects selective metathesis of the methyl moiety to afford the unprecedented halo-cyaphide complexes trans-[Ru(dppe)2(X)(CP)] (X = Cl, Br, I), which are structurally characterized (X = Cl, Br). Exemplified with the trans-bromide, these compounds are susceptible to substitution of the halides by nucleophilic reagents – illustrated with Me2Mg – and also readily undergo halide abstraction by TlOTf to afford the first hypo-coordinate cyaphide complex, viz. [Ru(dppe)2(CP)].OTf, which is isolable in bulk and exhibits good stability. NMR spectroscopic and crystallographic data reveal the latter to adopt a square pyramidal geometry with an accessible coordinate vacancy, which is susceptible to the addition of nucleophiles. This is illustrated analytically by reactions with Me2Mg and LiCCPh, and with its facile bulk carbonylation to afford trans-[Ru(dppe)2(CO)(CP)]+.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Research Centres and Groups: Energy and Materials Chemistry
Subjects: Q Science > QD Chemistry
Q Science > QD Chemistry > QD0146 Inorganic chemistry
Q Science > QD Chemistry > QD0901 Crystallography
Q Science > QD Chemistry > QD0901 Crystallography > QD0921 Crystal structure and growth
Depositing User: Ian Crossley
Date Deposited: 25 Oct 2019 10:56
Last Modified: 25 Oct 2019 10:56
URI: http://sro.sussex.ac.uk/id/eprint/87428

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Project NameSussex Project NumberFunderFunder Ref
Linearly Conjugated Phosphacarbon OrganometallicsG1810EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCILEP/N016785/1
EPSRC Doctoral Training Partnership 2016-17G1950EPSRC-ENGINEERING & PHYSICAL SCIENCES RESEARCH COUNCILEP/N509784/1
Polymetallaphosphacarbons: Toward phosphorus-doped organometallic molecular wiresG1182ROYAL SOCIETYUF120021