Metalcarbonylates of lanthanides. Unexpected formation of the trinuclear cluster [Na(DME)3]2[W3(CO)14]

3d–4f heterometallic complexes by the reduction of transition metal carbonyls with bulky LnII amidinates

“…Similar ν CO stretches (2017 to 1780 cm −1 ) have been observed in the related complex [Cp 2 Lu(thf ){Co(CO) 4 }]. 49 The solid-state structure was established by single-crystal X-ray crystallography (Fig. 2).…”

Reductive Trapping of [(OC)5W–W(CO)5]2− in a Mixed‐Valent SmII/III Calix[4]pyrrolide Sandwich

“…More frequently observed are positively charged W 2 (CO) 10 moieties in which negatively charged bridging co‐ligands enable a 18‐VE configuration to be achieved, for example, [W 2 (CO) 10 (μ‐CHPh)] . Both tungsten atoms of 1 are six‐coordinate with the two W(CO) 4 planes staggered, and the W−W bond length (3.1107(6) Å) is in the range of relevant tungsten carbonyl complexes, for example, six‐coordinate [Na(dme] 2 [W 3 (CO) 14 ] (2.79 Å) and seven‐coordinate [Cp*W(CO) 3 ] 2 (3.288(1) Å) . The bridging isocarbonyl C−O bond (1.201(10) Å) between Sm and W atoms is longer than the average of the terminal carbonyl C−O bonds (1.14 Å).…”

The ditungsten decacarbonyl dianion

“…Point (iii) contrasts to the situation found in I, 8 and for binary homobimetallic carbonyls generally. The W--W distance in 1 is 3.2421(8) Å, which is significantly longer than the values of 2.74 and 2.79(2) Å for the sum of the single bond covalent radii of two tungsten atoms 12 and II, 9 respectively, but it is closer to the W--W bond lengths of 3.1107(6) Å in I 8 and 3.2881(1) Å in [{(h 5 --C5Me5)W(CO)3}2]. 13 The W--C3 distance of 1.906(11) Å is shorter than the W--C2--5 distances (av.…”

“…7 Thus, after almost six decades a structure of free [(OC)5W--W(CO)5] 2-unperturbed by bridging ligands or stabilising counter cations has remained elusive, with the closest relative being homotrimetallic [Na(DME)3][(OC)5W--W(CO)4--W(CO)5] (II). 9 Here, as part of our ongoing studies into metal--metal bonding, 10 we report the synthesis, structural authentication, and characterisation of [(OC)5W--W(CO)5][K(18--crown--6)(THF)2]2 (1), completing the triad of structurally authenticated free group 6 homobimetallic binary metal-carbonyls. Surprisingly, the free [(OC)5W--W(CO)5] 2-dianion is found to adopt a perfectly D4h eclipsed geometry, instead of the D4d staggered form.…”