METAL-CARBONYL DERIVATIVES OF LANTHANIDES - CPLUCL2-INDUCED SYNTHESISOF THE TRINUCLEAR TUNGSTEN CLUSTER [NA(DME)3]2[W3(CO)14]

The cluster [Na(DME)3]2[W3(CO)14] (1) was prepared by treating CpLuCl2 with an equimolar mixture of Na2W(CO)5 and Na2W2(CO)10 in DME and cha racterized by X-ray analysis (Mo K(alpha) radiation, 653 reflections, R = 0.125). The crystals are rhombic, a = 18.749(4) angstrom, b = 15.0 74(3) angstrom, c = 9.505 (3) angstrom, Z = 2, space group C(mmm). The W-W distance in the W-W-W chain is 2.79 angstrom. The carbonyl ligand s at the tungsten atoms are eclipsed. Compound 1 is the first example of a homometallic carbonyl cluster of an early transition metal. It is suggested that CpLuCl2 interacts with Na2W(CO)5 to afford the highly reactive species {CpLu ... W(CO)5}, which further reacts with Na2W2(CO )10 to form 1.