Isocyanate Insertion into a La–P Phosphide Bond: A Versatile Route to Phosphaureate-Bridged Heterobimetallic Lanthanide–Coinage-Metal Complexes

[Image: see text] 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)(2)La(PHMes) (1) (with PN(–) = (N-(2-(diisopropylphosphanyl)-4-methylphenyl)-2,4,6-trimethylanilide) yields the phospha(thio)ureate complexes (PN)(2)La(OC(NPh)(PHMes)) (2) and (PN)(2)La(SC(NPh)(PHMes)) (3) with retention of the PH protons. Subsequent deprotonation of the phosphaureate complex 2 with potassium hexamethyldisilazide (KHMDS, K[N(SiMe(3))(2)]) leads to the polymeric complex [K{(PN)(2)La(OC(NPh)(PMes))}](n) (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,κ(2)(O,N):κ(1)(P)-phosphaureate bridging ligand. For an alternative route to complex 8 a direct protonolysis protocol between a new basic gold(I) precursor, namely ((Me)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).