Clusters containing carbene ligands—VI. The synthesis of higher nuclearity metal carbene cluster complexes by carbene ligand transfer. The synthesis and structures of [Ru 4(CO) 10{C(Ph)NMe 2}(μ 4-S) 2] and [Ru 4(CO) 10{C(Ph)NMe 2}(μ 4-S)(μ 5-S){W(CO) 5}

Abstract

UV irradiation of a solution of [Ru 4(CO) 11(μ 4-S) 2] ( 1) and [W(CO) 5{C(Ph)NMe 2}] yielded the two new higher nuclearity carbene-containing cluster complexes [Ru 4(CO) 10{C(Ph)NMe 2}(μ 4-S) 2] ( 2) 20%, and [Ru 4(CO) 10{C(Ph)NMe 2}(μ 4-S)(μ 5-S){W(CO) 5}] ( 3) 1%, by transfer of the carbene ligand from the tungsten complex to a ruthenium atom of the cluster. Compound 3 was obtained in 50% yield by UV irradiation of solutions of 2 and W(CO) 6. Compounds 2 and 3 were both characterized by single-crystal X-ray diffraction methods. Crystal data for 1: Ru 4S 2O 10NC 19H 11, M = 881.7, P2 1/ n, (No. 14), a = 11.847(1), b = 11.773(2), c = 19.310(2) Å, β = 104.685(8)°, V = 2597(1) Å 3, D c = 2.26 g cm −3, Z = 4, λ(Mo- K α) = 0.71069 Å (graphite monochromator), μ = 24.3 cm −1. Methods: MITHRIL, difference Fourier, full-matrix least-squares. Refinement of 3383 reflections ( F 2 ⩾ 3σ( F 2)), (1 ⩽ 2θ ⩽ 47°), gave R and R w values of 0.032 and 0.043. Data/parameters ratio = 10.4, highest peak in final difference Fourier = 0.82 e Å −3. Crystal data for 2: WRu 4S 2O 15NC 24H 11, M = 1205.6, monoclinic, P2 1/ n (No. 14), a = 15.268(1), b = 11.451(1), c = 19.121(2) Å, β = 99.731(8)°, V = 3295.0(6) Å 3, D c = 2.43 g cm −3, Z = 4, λ(Mo- K α), graphite monochromator, μ = 56.2. Methods: MITHRIL, difference Fourier, full-matrix least-squares. Refinement of 4444 reflections ( F 2 ⩾ 3σ( F 2)), (1 ⩽ 2θ ⩽ 48°), yielded R = 0.026, R w = 0.032. Data/parameters ratio = 10.5. Compound 2 consists of a square-planar cluster of four ruthenium atoms with two quadruply bridging sulphido ligands and one terminally coordinated phenyl(dimethylamino)carbene ligand. Compound 3 consists of a cluster of 2 with a W(CO) 5 group added to one of the quadruply bridging sulphido ligands.