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Updated: Dec 10, 2025

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Isocyanate Insertion into a La-P Phosphide Bond: A Versatile Route to Phosphaureate-Bridged Heterobimetallic
Fabian A Watt1, Nicole Dickmann1, Roland Schoch1
1Paderborn University, Faculty of Science, Department of Chemistry, Warburger Straße 100, 33098 Paderborn, Germany.
Abstract:
A new route to heterobimetallic lanthanide-coinage-metal complexes is disclosed. The selective insertion of organic substrates such as phenyl iso(thio)cyanate into the La-P bond of the primary phosphido complex (PN)La(PHMes) (1) (with PN- = (N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide) yields the phospha(thio)ureate complexes (PN)La(OC(NPh)(PHMes)) (2) and (PN)La(SC(NPh)(PHMes)) (3) with retention of the PH protons. Subsequent deprotonation of the phosphaureate complex 2 with potassium hexamethyldisilazide (KHMDS, K[N(SiMe3)2]) leads to the polymeric complex [K{(PN)La(OC(NPh)(PMes))}] (4). Complex 4 was found to be an excellent precursor for salt metathesis reactions with copper(I) and gold(I) chlorides supported by an N-heterocyclic carbene (NHC, 5 and 6) or a cyclic alkyl amino carbene (CAAC, 7 and 8). This resulted in the unprecedented formation of heterobimetallic lanthanum-coinage-metal complexes, containing the first example of a μ,κ2(O,N):κ1(P)-phosphaureate bridging ligand. For an alternative route to complex 8 a direct protonolysis protocol between a new basic gold(I) precursor, namely (CAAC)Au(HMDS), and 2 was also investigated. The complexes have been characterized by multinuclear NMR spectroscopy, IR spectroscopy, and X-ray crystallography (except for 8).
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