Palladium complexes with a tridentate PNO ligand. Synthesis of η1-allyl complexes and cross-coupling reactions promoted by boron compounds

Bruno Crociani; Simonetta Antonaroli; Marcello Burattini; Paola Paoli; Patrizia Rossi

doi:10.1039/B913130B

Palladium complexes with a tridentate PNO ligand. Synthesis of η¹-allyl complexes and cross-coupling reactions promoted by boron compounds†

Bruno Crociani,*^a Simonetta Antonaroli,^a Marcello Burattini,^a Paola Paoli^b and Patrizia Rossi^b

* Corresponding authors

^a Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata”, Via della Ricerca Scientifica, Roma, Italy
E-mail: crociani@stc.uniroma2.it
Fax: +39 06 72594328

^b Dipartimento di Energetica, Università di Firenze, Via S. Marta 3, Firenze, Italy

Abstract

The iminophosphine 2-(2-Ph₂P)C₆H₄N [double bond, length as m-dash] CHC₆H₄OH (P-N-OH) reacts with [Pd(μ-Cl)(η³-C₃H₅)]₂ yielding [PdCl(P-N-O)] and propene. In the presence of NEt₃, the reaction of P-N-OH with [Pd(μ-Cl)(η³-1-R¹,3-R²C₃H₃)]₂ (R¹ = R² = H, Ph; R¹ = H, R² = Ph) affords the η¹-allyl derivatives [Pd(η¹-1-R¹,3-R²C₃H₃)](P-N-O)] (R¹ = R² = H: 1; R¹ = H, R² = Ph: 2; R¹ = R² = Ph: 3). In solution, the complexes 1 and 3 undergo a slow dynamic process which interconverts the bonding site of the allyl ligand. The X-ray structural analysis of 1 indicates a square-planar coordination geometry around the palladium centre with a P,N,O,-tridentate ligand and a σ bonded allyl group. The complexes [PdR(P-N-O)] (R = C₆H₄Me-4, C [triple bond, length as m-dash] CPh) react slowly with p-bromoanisole in the presence of p-tolylboronic acid to give [PdBr(P-N-O)] and the coupling product RC₆H₄OMe-4. The latter reactions also proceed at a low rate under catalytic conditions. The coupling of allyl bromide with p-tolylboronic acid is catalyzed by [PdCl(P-N-O)]/K₂CO₃ to give 4-allyltoluene.

Supplementary files

Article information

DOI: https://doi.org/10.1039/B913130B
Article type: Paper
Submitted: 06 Jul 2009
Accepted: 27 Jan 2010
First published: 08 Mar 2010

Download Citation

Dalton Trans., 2010,39, 3665-3672

Permissions

Request permissions

Palladium complexes with a tridentate PNO ligand. Synthesis of η¹-allyl complexes and cross-coupling reactions promoted by boron compounds

B. Crociani, S. Antonaroli, M. Burattini, P. Paoli and P. Rossi, Dalton Trans., 2010, 39, 3665 DOI: 10.1039/B913130B

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.

Dalton Transactions