Abstract
Four new compounds having nine cluster electrons and cores of the types Mo3OCl3, Mo3OBr3, and W3OCl3 are reported. Compound (1) prepared by reduction of [Bu4N][Mo3OCl6(OAc)3] in THF with metallic zinc, was shown by X-ray crystallography to be Mo3OCl4(OAc)3 (THF)2 (1). It forms crystals in space groupP21 with unit cell dimensionsa=9.472(2) Å,b=13.546(4) Å,c=9.652(2) Å, β=101.70(2)°,V=1201(1) Å3,Z=2. The [Mo3(μ3-O)(μ-Cl)3]4+ core is surrounded by three μ-O2CCH3 anions, one Cl−, and two THF and has Mo-Mo distances of 2.620(1) Å, 2.613(1) Å, and 2.530(1) Å, with the shortest bond between the two Mo atoms to which the THF molecules are coordinated. Compounds [Bu4N]2 [Mo3OBr6(O2CCH3)3] · Me2CO, (2) and [Mo3OBr3(O2CCH3)3(PMe3)3]3 · BF4, (3) are the first two nine-electron Mo3 species with a [Mo3(μ3-O) Br3]4+ core. Both were obtained by zinc reduction of [Mo3OBr6(O2CCH3)3]− in the presence of (NBu4) Br (2) or PMe3 and NaBF4 (3), and each was characterized crystallographically. Compound (2) crystallized in space group Cc with unit cell dimensionsa=25.037(5) Å,b=12.827(2) Å,c=21.484(4) Å, β=122.96(1)0,V=5790(3) Å3,Z=4. While the anion has no crystallographically required symmetry, its virtual symmetry is C3v . The Mo-Mo distances are 2.619(2) Å, 2.610(3) Å, 2.644(2) Å, with a mean value of 2.624[14] Å. Compound (3) crystallized in space groupP21/c with unit cell dimensionsa=10.846(2) Å,b=25.033(5) Å,c=12.641(5) Å, β=94.74(2)0,V=3420(2) Å3,Z=4. The cation occupies a general position but has virtual C3v symmetry, with Mo-Mo distances of 2.601(2) Å, 2.610(2) Å, 2.627(2) Å, with a mean value of 2.613[14] Å. Thus the anionic and cationic Mo3 clusters in (2) and (3), respectively, have average Mo-Mo distances that are equal within experimental error. Compound (4), [NEt4]2 [W3OCl6(O2CCH3)3] is the first 9-electron compound of this type containing tungsten. It was prepared by reduction of [Et4N][W3OCl6(OAc)3] in benzene with Na/Hg. It crystallized in space groupP212121 with unit cell dimensionsa=11.076(2) Å,b=14.345(2) Å,c=21.026(3) Å,V=3574(1) Å3,Z=4. The anion resides on a general position but has virtual C3v symmetry, with W-W distances of 2.577(1) Å, 2.612(1) Å, 2.584(1) Å and a mean value of 2.591[15] Å.
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Cotton, F.A., Shang, M. & Sun, Z.S. Further studies of M3(μ3-O)(μ-X)3(μ-O2CCH3)3L3 (M=Mo, W) type clusters with nine core electrons. J Clust Sci 3, 123–144 (1992). https://doi.org/10.1007/BF00702878
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DOI: https://doi.org/10.1007/BF00702878