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Issue 6, 2018
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Contiguous multiple π-coordination of π-conjugated polyenes: bonding nature and charge delocalization behaviour of polyene–(palladium chain) sandwich clusters

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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

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Publication details

The article was received on 01 Oct 2017, accepted on 08 Jan 2018 and first published on 25 Jan 2018


Article type: Paper
DOI: 10.1039/C7CP06735F
Citation: Phys. Chem. Chem. Phys., 2018,20, 4287-4296
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    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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