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A Phosphine Functionalized β-Diketimine Ligand for the Synthesis of Manifold Metal Complexes.

Chemistry (Weinheim an der Bergstrasse, Germany) (2020-04-15)
Christina Zovko, Sebastian Bestgen, Christoph Schoo, Anne Görner, Jose M Goicoechea, Peter W Roesky
ABSTRACT

A bis(diphenyl)-phosphine functionalized β-diketimine (PNac-H) was synthesized as a flexible ligand for transition metal complexes. The newly designed ligand features symmetrically placed phosphine moieties around a β-diketimine unit, forming a PNNP-type pocket. Due to the hard and soft donor atoms (N vs. P) the ligand can stabilize various coordination polyhedra. A complete series ranging from coordination numbers 2 to 6 was realized. Linear, trigonal planar, square planar, tetrahedral, square pyramidal, and octahedral coordination arrangements containing the PNac-ligand around the metal center were observed by using suitable metal sources. Hereby, PNac-H or its anion PNac- acts as mono-, bi- and tetradendate ligand. Such a broad flexibility is unusual for a rigid tetradentate system. The structural motifs were realized by treatment of PNac-H with a series of late transition metal precursors, for example, silver, gold, nickel, copper, platinum, and rhodium. The new complexes have been fully characterized by single crystal X-ray diffraction, NMR, IR, UV/Vis spectroscopy, mass spectrometry as well as elemental analysis. Additionally, selected complexes were investigated regarding their photophysical properties. Thus, PNac-H proved to be an ideal ligand platform for the selective coordination and stabilization of various metal ions in diverse polyhedra and oxidation states.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Diphenylphosphine, 98%
Sigma-Aldrich
Potassium, chunks (in mineral oil), 98% trace metals basis
Sigma-Aldrich
Copper(I) chloride, AnhydroBeads, ≥99.99% trace metals basis
General Purpose Viscosity Standard; UKAS ISO/IEC17025 and ISO 17034 certified, viscosity 4599 mPa.s (25 °C)