Metalloligands containing aminofulvene-aldiminate (AFA) ligands and their bimetallic complexes

Philip J. Bailey; Mahmudur Rahman; Simon Parsons; Muhammad R. Azhar; Fraser J. White

doi:10.1039/c2dt32804f

Metalloligands containing aminofulvene-aldiminate (AFA) ligands and their bimetallic complexes

Philip J. Bailey^*, Mahmudur Rahman, Simon Parsons, Muhammad R. Azhar, Fraser J. White

^*Corresponding author for this work

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

Abstract / Description of output

A simple and convenient route to η⁵-coordinated Ru and Rh aminofulvene-aldiminate (AFA) complexes is described. The metalloligands [Cp*Ru{η⁵-(Ph₂AFAH)}][BF₄] (3), [Cp*Ru{η⁵-(benzyl₂AFAH)}][OTf] (7), [Cp*Rh{η⁵-(Cy₂AFA)H}][BF₄]₂ (8) and [Cp*Rh{η⁵-(Cy₂AFA)}][BF₄] (9) have been synthesised and characterised. The basicity of 9 has been found to be significantly less than its neutral analogue and thus eliminates the need for a deprotonation step to ligate to a second metal in the κ²-N,N′-coordination mode. The reaction of 9 with a palladium precursor provides a mixed-metal complex [Cp*Rh(η⁵/κ²-Cy₂AFA)PdCl₂][BF₄] (12). Cyclic voltammetry studies of the Ph₂AFAH ligand shows an irreversible one electron oxidation peak at +1.0 V (vs. Fc/Fc⁺). Complex 3 shows an irreversible oxidation at +1.5 V and a reduction peak at −1.0 V. The oxidation of 3 occurs on the AFA ligand backbone whereas the structurally analogous neutral 1,2-bis(imidoyl)pentamethyl-ruthenocene shows reversible oxidation at the Ru center.

Original language	English
Pages (from-to)	2879-2886
Number of pages	8
Journal	Dalton Transactions
Volume	42
Issue number	8
DOIs	https://doi.org/10.1039/c2dt32804f
Publication status	Published - 2013

Keywords / Materials (for Non-textual outputs)

ORGANOMETALLIC CHEMISTRY
TRANSITION METALS
DERIVATIVES
CATALYSTS
ETHYLENE
RHODIUM
COBALT

Access to Document

10.1039/c2dt32804f

http://pubs.rsc.org/en/Content/ArticleLanding/2013/DT/c2dt32804f#!divAbstract

Cite this

@article{b478436d123a41f6b331c4b0a2b935af,

title = "Metalloligands containing aminofulvene-aldiminate (AFA) ligands and their bimetallic complexes",

abstract = "A simple and convenient route to η5-coordinated Ru and Rh aminofulvene-aldiminate (AFA) complexes is described. The metalloligands [Cp*Ru{η5-(Ph2AFAH)}][BF4] (3), [Cp*Ru{η5-(benzyl2AFAH)}][OTf] (7), [Cp*Rh{η5-(Cy2AFA)H}][BF4]2 (8) and [Cp*Rh{η5-(Cy2AFA)}][BF4] (9) have been synthesised and characterised. The basicity of 9 has been found to be significantly less than its neutral analogue and thus eliminates the need for a deprotonation step to ligate to a second metal in the κ2-N,N′-coordination mode. The reaction of 9 with a palladium precursor provides a mixed-metal complex [Cp*Rh(η5/κ2-Cy2AFA)PdCl2][BF4] (12). Cyclic voltammetry studies of the Ph2AFAH ligand shows an irreversible one electron oxidation peak at +1.0 V (vs. Fc/Fc+). Complex 3 shows an irreversible oxidation at +1.5 V and a reduction peak at −1.0 V. The oxidation of 3 occurs on the AFA ligand backbone whereas the structurally analogous neutral 1,2-bis(imidoyl)pentamethyl-ruthenocene shows reversible oxidation at the Ru center.",

keywords = "ORGANOMETALLIC CHEMISTRY, TRANSITION METALS, DERIVATIVES, CATALYSTS, ETHYLENE, RHODIUM, COBALT",

author = "Bailey, {Philip J.} and Mahmudur Rahman and Simon Parsons and Azhar, {Muhammad R.} and White, {Fraser J.}",

year = "2013",

doi = "10.1039/c2dt32804f",

language = "English",

volume = "42",

pages = "2879--2886",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "8",

}

TY - JOUR

T1 - Metalloligands containing aminofulvene-aldiminate (AFA) ligands and their bimetallic complexes

AU - Bailey, Philip J.

AU - Rahman, Mahmudur

AU - Parsons, Simon

AU - Azhar, Muhammad R.

AU - White, Fraser J.

PY - 2013

Y1 - 2013

N2 - A simple and convenient route to η5-coordinated Ru and Rh aminofulvene-aldiminate (AFA) complexes is described. The metalloligands [Cp*Ru{η5-(Ph2AFAH)}][BF4] (3), [Cp*Ru{η5-(benzyl2AFAH)}][OTf] (7), [Cp*Rh{η5-(Cy2AFA)H}][BF4]2 (8) and [Cp*Rh{η5-(Cy2AFA)}][BF4] (9) have been synthesised and characterised. The basicity of 9 has been found to be significantly less than its neutral analogue and thus eliminates the need for a deprotonation step to ligate to a second metal in the κ2-N,N′-coordination mode. The reaction of 9 with a palladium precursor provides a mixed-metal complex [Cp*Rh(η5/κ2-Cy2AFA)PdCl2][BF4] (12). Cyclic voltammetry studies of the Ph2AFAH ligand shows an irreversible one electron oxidation peak at +1.0 V (vs. Fc/Fc+). Complex 3 shows an irreversible oxidation at +1.5 V and a reduction peak at −1.0 V. The oxidation of 3 occurs on the AFA ligand backbone whereas the structurally analogous neutral 1,2-bis(imidoyl)pentamethyl-ruthenocene shows reversible oxidation at the Ru center.

AB - A simple and convenient route to η5-coordinated Ru and Rh aminofulvene-aldiminate (AFA) complexes is described. The metalloligands [Cp*Ru{η5-(Ph2AFAH)}][BF4] (3), [Cp*Ru{η5-(benzyl2AFAH)}][OTf] (7), [Cp*Rh{η5-(Cy2AFA)H}][BF4]2 (8) and [Cp*Rh{η5-(Cy2AFA)}][BF4] (9) have been synthesised and characterised. The basicity of 9 has been found to be significantly less than its neutral analogue and thus eliminates the need for a deprotonation step to ligate to a second metal in the κ2-N,N′-coordination mode. The reaction of 9 with a palladium precursor provides a mixed-metal complex [Cp*Rh(η5/κ2-Cy2AFA)PdCl2][BF4] (12). Cyclic voltammetry studies of the Ph2AFAH ligand shows an irreversible one electron oxidation peak at +1.0 V (vs. Fc/Fc+). Complex 3 shows an irreversible oxidation at +1.5 V and a reduction peak at −1.0 V. The oxidation of 3 occurs on the AFA ligand backbone whereas the structurally analogous neutral 1,2-bis(imidoyl)pentamethyl-ruthenocene shows reversible oxidation at the Ru center.

KW - ORGANOMETALLIC CHEMISTRY

KW - TRANSITION METALS

KW - DERIVATIVES

KW - CATALYSTS

KW - ETHYLENE

KW - RHODIUM

KW - COBALT

U2 - 10.1039/c2dt32804f

DO - 10.1039/c2dt32804f

M3 - Article

SN - 1477-9226

VL - 42

SP - 2879

EP - 2886

JO - Dalton Transactions

JF - Dalton Transactions

IS - 8

ER -

Metalloligands containing aminofulvene-aldiminate (AFA) ligands and their bimetallic complexes

Abstract / Description of output

Keywords / Materials (for Non-textual outputs)

Access to Document

Fingerprint

Cite this