Issue 35, 2019

Diferrocenylmercury diphosphine diastereomers with unique geometries: trans-chelation at Pd(ii) with short Hg(ii)⋯Pd(ii) contacts

Abstract

Diphosphine chelate ligands are essential in many catalytic processes with both the electronic structure and bite angle having a dramatic influence on the coordination behavior and catalytic performance. The synthesis of a new class of diferrocenylmercury-supported diphosphine chelate ligands was accomplished by the reaction of (ortho-diphenylphosphino)ferrocenyl sulfinate (2) with t-BuLi, followed by treatment with mercury(II) chloride. Two diastereomers, 4a (pSpR-, meso-isomer) and 4b (pSpS-isomer), differ in the orientation of the ferrocene moiety relative to the central Ph2PC5H3-Hg-C5H3PPh2 bridging entity. They were isolated independently and fully characterized in solution and in the solid state by single crystal X-ray diffraction analysis. Key characteristics of these ligands are their exceptionally wide and flexible bite angles and the unique stereochemical environment that is achieved upon coordination to transition metals. Complexation to Pd(II)Cl2 gives rise to unusual square-planar trans-chelate complexes 5a (meso) and 5b (pSpS). In competition reactions, 4a and 4b show similar reactivity toward Pd(II)Cl2. The molecular structures of 5a and 5b exhibit short Pd⋯Hg contacts, possibly indicating secondary metallophilic interactions as further evidenced by bond-critical points between Pd and Hg that were identified by AIM analyses.

Graphical abstract: Diferrocenylmercury diphosphine diastereomers with unique geometries: trans-chelation at Pd(ii) with short Hg(ii)⋯Pd(ii) contacts

Supplementary files

Article information

Article type
Paper
Submitted
30 Jun 2019
Accepted
15 Aug 2019
First published
15 Aug 2019

Dalton Trans., 2019,48, 13430-13439

Author version available

Diferrocenylmercury diphosphine diastereomers with unique geometries: trans-chelation at Pd(II) with short Hg(II)⋯Pd(II) contacts

A. C. Tagne Kuate, R. A. Lalancette, T. Bannenberg, M. Tamm and F. Jäkle, Dalton Trans., 2019, 48, 13430 DOI: 10.1039/C9DT02728A

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