Synthesis and reactions of tetrahedral (μ3-S)FeCoMo and (μ3-Se)FeCoMo cluster complexes containing (p-CH3OC6H4)2Te ligands. X-ray structure of (μ3-S)FeCoMo(CO)7(PPh3)[η5-C5H4C(O)C2H4CO2 C2H5]

While the single tetrahedral cluster (μ3-S)FeCoMo(CO)8[η5-C5H4C(O)C2H4CO2 C2H5] (1) prepared from (μ3-S)FeCo2(CO)9 and Na[Mo(CO)3(η5-C5H4C(O)C2H4CO2 C2H5)] reacts with (p-CH3OC6H4)2TeO (BMPTO) through oxygen transfer reaction to give mono-(p-CH3OC6H4)2Te (BMPT)-substituted cluster (μ3-S)FeCoMo(CO)7(BMPT) [η5-C5H4C(O)C2H4CO2C2H5] (2), the double tetrahedral cluster [(μ3-S)FeCoMo(CO)8]2 [η5-C5H4C(O)CH2]2 (3) prepared from (μ3-S)FeCo2(CO)9 and Na2[Mo(CO)3(η5-C5H4 C(O)CH2)]2 reacts with BMPTO to afford mono- and bis-BMPT-substituted clusters [(μ3-S)FeCoMo(CO)7(BMPT)][η5-C5H4C(O)CH2]2[(μ3-S)FeCoMo(CO)8] (4) and [(μ3-S)FeCoMo(CO)7 (BMPT)]2[η5-C5H4C(O)CH2]2 (5). Similarly, while the double cluster [(μ3-Se)FeCoMo(CO)8]2[η5-C5H4C(O)CH2]2 (6) reacts with BMPTO to give mono- and bis-BMPT-substituted clusters [(μ3-Se)FeCoMo(CO)7(BMPT)][η5-C5H4C(O)CH2]2[(μ3-Se)FeCoMo(CO)8] (7) and [(μ3-Se)FeCoMo(CO)7(BMPT)]2[η5-C5H4C(O)CH2]2 (8), reaction of [(μ3-S)FeCoMo(CO)8]2[(η5-C5H4C2H4)2O] (9) with BMPTO affords corresponding mono- and bis-BMPT-substituted clusters [(μ3-S)FeCoMo(CO)7 (BMPT)][(η5-C5H4C2H4)2O][(μ3-S)FeCoMo(CO)8] (10) and [(μ3-S)FeCoMo(CO)7 (BMPT)]2[(η5-C5H4C2H4)2O] (11). It is interesting to note that the BMPT ligands in clusters 2 and 5 can be selectively substituted by PPh3 to give mono-PPh3-substituted cluster (μ3-S)FeCoMo(CO)7(PPh3)[η5-C5H4C(O)C2H4CO2C2H5] (12), and bis-PPh3-substituted cluster [(μ3-S)FeCoMo(CO)7(PPh3)]2[η5-C5H4C(O)CH2]2 (13), respectively. The molecular structure of 12 has been determined by X-ray diffraction techniques, which provides the evidence for that the BMPT ligands in those above BMPT-substituted products being attached to the cobalt atoms.