119455-66-2Relevant academic research and scientific papers
Conformational preferences in six-coordinate, octahedral complexes of molybdenum(III). Synthesis and structure of MoX3(dppe)L [X = Cl, Br, I; dppe = bis(diphenylphosphino)ethane; L = tetrahydrofuran, acetonitrile, trimethylphosphine]
Owens, Beth E.,Poli, Rinaldo,Rheingold, Arnold L.
, p. 1456 - 1462 (2008/10/08)
MoBr3(THF)3 can be obtained in large scale and high yields by bromination of Mo2Br4(CO)8 in tetrahydrofuran (THF). The ligand replacement reaction of MoX3(THF)3 with bis(diphenylphosphino)ethane (dppe) in THF as solvent affords the mononuclear MoX3(dppe)(THF) compounds. An X-ray crystal structure investigation of the iodide derivative shows an octahedral structure with a meridional arrangement of the three iodo ligands. Crystal data: monoclinic, space group P21/n, a = 24.049 (4) ?, b = 12.283 (2) ?, c = 12.985 (2) ?, β = 99.94 (2)°, V = 3778.1 (2) ?3, Z = 4, dc = 1.79 g cm-3, μ(Mo Kα) = 29.34 cm-1, R = 0.0361, Rw = 0.0517 for 354 parameters and 3589 observations with F02 > 3σ(F02). The remaining THF ligand in MoX3(dppe)(THF) can be replaced with MeCN or PMe3 but not with P(n-Bu)3, PPh3, or dppe. The X-ray crystal structure of MoI3(dppe)(PMe3) shows an octahedral geometry with a facial arrangement of the three iodo ligands. Crystal data: orthorhombic, space group Pnma, a = 15.413 (4) ?, b = 21.786 (4) ?, c = 9.787 (1) ?, V = 3286 (2) ?3, Z = 4, dc = 1.92 g cm-3, μ(Cu Kα) = 274.81 cm-1, R = 0.080, Rw = 0.080 for 154 parameters and 1091 observations with F02 > 3σ(F02). For comparison purposes, a crystallographic study of mer-MoI3(PMe3)3 has also been carried out. Crystal data: tetragonal, space group I41/a, a = 18.379 (5) ?, c = 26.257 (5) ?, V = 8896 (4) ?3, Z = 16, dc = 2.11 g cm-3, μ(Mo Kα) = 47.62 cm-1, R = 0.064, Rw = 0.074 for 145 parameters and 1854 observations with F02 > 2.5σ(F02). The conformational preference in these octahedral Mo(III) complexes is discussed in terms of the steric interactions between the neutral ligands.
