Calix[4]pyrrolato Stannate(II): A Tetraamido Tin(II) Dianion and Strong Metal-Centered σ-Donor

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 Jan 12

PMID 35019214

Authors

Heiko Ruppert

Lutz Greb

Affiliations

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Abstract

Anionic, metal-centered nucleophiles are emerging compounds with unique reactivities. Here, we describe the isolation and full characterization of the first tetraamido tin(II) dianion, its behavior as ligand towards transition metals, and its reactivity as a tin-centered nucleophile. Experimental values such as the Tolman electronic parameter (TEP) and computations attest tin-located σ-donor ability exceeding that of carbenes or electron-rich phosphines. Against transition metals, the stannate(II) can act as η - or η -type ligand. With aldehydes, it reacts by hydride substitution to give valuable acyl stannates. The reductive dehalogenation of iodobenzene indicates facile redox pathways mediated by halogen bond interaction. Calix[4]pyrrolato stannate(II) represents the first example of this macrocyclic ligand in low-valent p-block element chemistry.

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