Compounds of the general formula [NR4]n[M(CO)3(XR)]n (n = 3 or 4) (M = Cr, Mo, W; XR = OMe, OEt, SPh) have been prepared by refluxing the corresponding M(CO)3PMTA (PMTA = 1,1,4,7,7-pentamethyldiethylenetriamine) with the appropriate NaXR in THF, followed by metathesis with tetramethyl- or tetraethylammonium halides. Treatment of W(CO)3PMTA or W(CO)3(CH3CN)3 with NaOPh provides after cation exchange a substance formulated as [Et4N]3[W2(CO)6(μ-OPh)3]. These complexes have been characterized by infrared and 1H NMR spectra and elemental analyses. Also, the product obtained from the reaction of NaOEt with W(CO)3PMTA followed by metathesis with Me4NBr has been characterized by a single-crystal X-ray structure determination. This material has the formula [Me4N]3[W3(CO)9(μ-OEt)(μ3-OEt)2]. The anion contains a highly unsymmetrical metal triangle which is best considered to contain only one W—W bond. The molecule crystallizes in space group Cc (No. 9) with two crystallographically independent molecules in the unit cell. Crystal data: a = 14.831 (4) Å, b = 41.686 (14) Å, c = 12.905 (3) Å, β = 90.74 (4)∘, Z = 4, V = 7978 (7) Å3, and ρ(calcd) = 1.848 g/cm3.