Calix[4]pyrrolato Stannate(II): A Tetraamido Tin(II) Dianion and Strong Metal‐Centered σ‐Donor
Open Access
- 7 February 2022
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 61 (13) , e202116615
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 η1‐ or η5‐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.Keywords
Funding Information
- H2020 European Research Council (948708)
This publication has 123 references indexed in Scilit:
- Coordination Chemistry of Cyclic Disilylated Stannylenes and Plumbylenes to Group 4 MetallocenesJournal of the American Chemical Society, 2012
- Intramolecularly coordinated heteroleptic organostannylene tungsten pentacarbonyl complexes 4-tBu-2,6-[P(O)(OiPr)2]2C6H2Sn(X)W(CO)5 (X = Cl, F, PPh2, PPh2[W(CO)5]). Syntheses and reactivityDalton Transactions, 2011
- π-Metal complexes of tetrapyrrolic systems. A novel coordination mode in “porphyrin-like” chemistryChemical Society Reviews, 2009
- Multielectron Redox Chemistry of Iron PorphyrinogensJournal of the American Chemical Society, 2005
- Acid−Base Chemistry of the Metal-Bonded Porphyrinogen Tetraanion: A Novel Methodology for the Metal-Assisted Deuteration, Alkylation, and Functionalization of the Porphyrinogen SkeletonJournal of the American Chemical Society, 1998
- Macrocyclic (C22H22N4) complexes of germanium(II), tin(II), gallium(III), and indium(III). Main group functionalities in unusual environmentsInorganic Chemistry, 1992
- Synthesis and chemistry of B11H11Sn2- and its germanium and lead analogs. Crystal structure of [B11H11SnCH3]PPh3CH3.cntdot.CH2Cl2Inorganic Chemistry, 1992
- A general access to acylstannanesThe Journal of Organic Chemistry, 1989
- Sources of hydrogen in the electrochemical reduction of iodobenzene in dimethylformamide solutionJournal of the American Chemical Society, 1979
- Evidence for a radical mechanism of aromatic "nucleophilic" substitutionJournal of the American Chemical Society, 1970