The First Triangular Trinuclear Cluster Compounds of Molybdenum with Nine Cluster Electrons: 1-n, n = 1-3

Article abstract of DOI:10.1021/ja00018a030

The first four M3X13 type molybdenum triangular trinuclear cluster compounds with nine cluster electrons are described in this paper: (Bu4N)2*Me2CO (1), (Bu4N)*2THF (2), (3), and *THF (4).The first three compounds were obtained by chemical reduction of (Bu4N)*Me2CO, and the last one was prepared as a byproduct from a reaction mixture containing MoCl3(THF)3, Na/Hg, S, NaOAc, and PMe3.In all four compounds, each metal atom has the formal oxidation state + 3 and there are nineelectrons for the metal cluster.Physical measurements indicated that these compounds are paramagnetic and have one unpaired electron, which is in good accord with theoretical calculations.In compound 1 the metal-metal bond distances are 2.617 (1), 2.598 (1), and 2.598 (1) Angstroem.The crystals belong to the space group Cc with Z = 4.The unit cell dimensions are a = 22.600 (3) Angstroem, b = 12.031 (2) Angstroem, c = 23.110 (4) Angstroem, β = 113.51 (1) deg, V = 5762 (2) Angstroem³.In compound 2, the metal-metal bond distances are 2.637 (1), 2.573 (1), and 2.567 (1) Angstroem.It crystallized in the space group P2₁/c with Z = 4 and the following unit cell dimensions a = 13.419 (3) Angstroem, b = 19.882 (5) Angstroem, c = 18.630 (5) Angstroem, β = 96.27 (2) deg, V = 4940 (2) Angstroem³.Compound 3 belongs to the space group P2₁/c with a = 10.381 (3) Angstroem, b = 12.680 (2) Angstroem, c = 19.402 (2) Angstroem, β = 90.09 (1) deg, V = 2553.6 (8) Angstroem³, and Z = 4.The metal-metal bond distances are 2.5878 (5), 2.6117 (5), and 2.5764 (5) Angstroem.Compound 4 forms triclinic crystals in the space group P<*>1 with the following unit cell dimensions a = 10.121 (2) Angstroem, b = 11.013 (2) Angstroem, c = 14.628 (3) Angstroem α = 97.71 (2) deg, β = 93.06 (2) deg, γ = 104.62 (2) deg, V = 1556.9 (6) Angstroem³, and Z = 2.The metal-metal bond distances are 2.597 (1), 2.608 (1), and 2.5673 (9) Angstroem.