Issue 45, 2010
From the journal:

Dalton Transactions

Cationic Diiron and Dirutheniumμ-Allenyl Complexes: Synthesis, X-Ray Structures and Cyclization Reactions with Ethyldiazoacetate/Amine Affording Unprecedented Butenolide- and Furaniminium-Substituted Bridging Carbene Ligands†

Adriano Boni,ab   Fabio Marchetti,‡a   Guido Pampaloni*a  and  Stefano Zacchinic  

* Corresponding authors

a Università di Pisa, Dipartimento di Chimica e Chimica Industriale, Via Risorgimento 35, Pisa, Italy
E-mail: pampa@dcci.unipi.it
Fax: +39 050 2219246
Tel: +39 050 2219219

b Scuola Normale Superiore, Piazza dei Cavalieri, Pisa, Italy

c Università di Bologna, Dipartimento di Chimica Fisica e Inorganica, Viale Risorgimento 4, Bologna, Italy

Abstract

The novel cationic diiron μ-allenyl complexes [Fe2Cp2(CO)2(μ-CO){μ-η1:η2α,β-Cα(H)[double bond, length as m-dash]Cβ[double bond, length as m-dash]Cγ(R)2}]+ (R = Me, 4a; R = Ph, 4b) have been obtained in good yields by a two-step reaction starting from [Fe2Cp2(CO)4]. The solid state structures of [4a][CF3SO3] and of the diruthenium analogues [Ru2Cp2(CO)2(μ-CO){μ-η1:η2α,β-Cα(H)[double bond, length as m-dash]Cβ[double bond, length as m-dash]Cγ(R)2}][BPh4] (R = Me, [2a][BPh4]; R = Ph, [2c][BPh4]) have been ascertained by X-ray diffraction studies. The reactions of 2c and 4a with Brønsted bases result in formation of the μ-allenylidene compound [Ru2Cp2(CO)2(μ-CO){μ-η1:η1-Cα[double bond, length as m-dash]Cβ[double bond, length as m-dash]Cγ(Ph)2}] (5) and of the dimetallacyclopentenone [Fe2Cp2(CO)(μ-CO){μ-η1:η3-Cα(H)[double bond, length as m-dash]Cβ(Cγ(Me)CH2)C([double bond, length as m-dash]O)}] (6), respectively. The nitrile adducts [Ru2Cp2(CO)(NCMe)(μ-CO){μ-η1:η2-Cα(H)[double bond, length as m-dash]Cβ[double bond, length as m-dash]Cγ(R)2}]+ (R = Me, 7a; R = Ph, 7b), prepared by treatment of 2a,c with MeCN/Me3NO, react with N2CHCO2Et/NEt3 at room temperature, affording the butenolide-substituted carbene complexes [Ru2Cp2(CO)(μ-CO){μ-η1:η3-Cα(H)[upper bond 1 start]CβCγ(R)2OC([double bond, length as m-dash]O)C[upper bond 1 end](H)] (R = Me, 10a; R = Ph, 10b). The intermediate cationic compound [Ru2Cp2(CO)(μ-CO){μ-η1:η3-Cα(H)[upper bond 1 start]CβCγ(Me)2OC(OEt)C[upper bond 1 end](H)]+ (9) has been detected in the course of the reaction leading to 10a. The addition of N2CHCO2Et/NHEt2 to 7a gives the 2-furaniminium-carbene [Ru2Cp2(CO)(μ-CO){μ-η1:η3-Cα(H)[upper bond 1 start]CβCγ(Me)2OC(OEt)C[upper bond 1 end](H)]+ (11). The X-ray structures of 10a, 10b and [11][BF4] have been determined. The reactions of 4a,b with MeCN/Me3NO result in prevalent decomposition to mononuclear iron species.

Graphical abstract: Cationic Diiron and Diruthenium μ-Allenyl Complexes: Synthesis, X-Ray Structures and Cyclization Reactions with Ethyldiazoacetate/Amine Affording Unprecedented Butenolide- and Furaniminium-Substituted Bridging Carbene Ligands

About
Cited by
Related
Download options Please wait...

Supplementary files

Article information

DOI
https://doi.org/10.1039/C0DT00697A
Article type
Paper
Submitted
22 Jun 2010
Accepted
26 Aug 2010
First published
18 Oct 2010

Dalton Trans., 2010,39, 10866-10875

Permissions

Request permissions

Cationic Diiron and Diruthenium μ-Allenyl Complexes: Synthesis, X-Ray Structures and Cyclization Reactions with Ethyldiazoacetate/Amine Affording Unprecedented Butenolide- and Furaniminium-Substituted Bridging Carbene Ligands

A. Boni, F. Marchetti, G. Pampaloni and S. Zacchini, Dalton Trans., 2010, 39, 10866 DOI: 10.1039/C0DT00697A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements