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Issue 96, 2016
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Zero-valent isocyanides of nickel, palladium and platinum as transition metal σ-type Lewis bases

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Abstract

Transition metal complexes that contain metal-to-ligand retrodative σ-bonds have become the subject of increasing studies over the last decade. Lewis acidic “Z-type ligands” can modulate the electronic structure of their resultant complexes in a manner distinct from 2e donor ligands, and can also engage in cooperative reactivity with a Lewis basic transition metal. In this Feature article, we summarize our work with transition metal isocyanide complexes of group 10 metals that have exploited metal-based σ-type Lewis basicity. While the complexes Ni(CNArMes2)3, Pd(CNArDipp2)2 and Pt(CNArDipp2)2 were initially targeted as analogues to unstable, low-coordinate metal carbonyls, it soon became apparent that these zero-valent metal centers bore appreciable Lewis basic qualities due largely to the enhanced σ-donor/π-acid ratio of isocyanides compared to CO. Detailed spectroscopic and structural studies of metal-only Lewis pairs (MOLPs) formed from these complexes have furthered our understanding of the electronic structure perturbations effected by Z-type ligand binding. In addition, the platinum (boryl)iminomethane (BIM) complex Pt(κ2-N,B-Cy2BIM)(CNArDipp2) has illuminated a general ligand design strategy that can engender significant reverse-dative interactions with buttressed Lewis acids, and also has expanded the known scope of cooperative reactivity that can be realized at a transition metal–borane linkage.

Graphical abstract: Zero-valent isocyanides of nickel, palladium and platinum as transition metal σ-type Lewis bases

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Publication details

The article was received on 27 Sep 2016, accepted on 27 Oct 2016 and first published on 27 Oct 2016


Article type: Feature Article
DOI: 10.1039/C6CC07863J
Citation: Chem. Commun., 2016,52, 13829-13839
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    Zero-valent isocyanides of nickel, palladium and platinum as transition metal σ-type Lewis bases

    B. R. Barnett and J. S. Figueroa, Chem. Commun., 2016, 52, 13829
    DOI: 10.1039/C6CC07863J

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