Issue 6, 2018

Contiguous multiple π-coordination of π-conjugated polyenes: bonding nature and charge delocalization behaviour of polyene–(palladium chain) sandwich clusters

Abstract

The contiguous multiple π-coordination (CMπC) bonds are formed at the molecular interface between the extended π-conjugated sp2-carbon framework and metal–metal moieties. However, the static properties including the bonding nature of the CMπC bonds have not been well-understood. Here we report the charge delocalization behavior and bonding nature of the polyene–(palladium chain) sandwich clusters. We observed the chain-length dependent 13C NMR chemical shifts of the terminal phenyl groups in [Pdm{Ph(CH[double bond, length as m-dash]CH)m+1Ph}2][B(ArF)4]2 (m = 3, 4, 5, 6), showing the efficient delocalization of positive charge over the polyene ligands. Furthermore, the detailed molecular orbital analysis of several model clusters provides insights into the bonding nature of the μ-η2:(η2:)nη2- and μ-η3:(η2:)nη3-poylene palladium chain sandwich clusters, where the former type is attributed to the corner-sharing Pd array and the latter to the edge-sharing/corner-sharing hybrid Pd array. The analogy of the μ-η3:(η2:)nη3-type with the carbonyl-bridge coordination is discussed. The Pd string in each mode of sandwich chain clusters has a weak M–M bonding interaction.

Graphical abstract: Contiguous multiple π-coordination of π-conjugated polyenes: bonding nature and charge delocalization behaviour of polyene–(palladium chain) sandwich clusters

Supplementary files

Article information

Article type
Paper
Submitted
01 out 2017
Accepted
08 jan 2018
First published
25 jan 2018

Phys. Chem. Chem. Phys., 2018,20, 4287-4296

Contiguous multiple π-coordination of π-conjugated polyenes: bonding nature and charge delocalization behaviour of polyene–(palladium chain) sandwich clusters

M. Yamane, M. Yamashita, K. Yamamoto and T. Murahashi, Phys. Chem. Chem. Phys., 2018, 20, 4287 DOI: 10.1039/C7CP06735F

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