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 (mu (3)-S)FeCoMo(CO)(8)[eta (5)-C5H4C(O)C2H4CO2 C2H5] (1) prepared from (mu (3)-S)FeCo2(CO)(9) and Na[Mo(CO)(3)(eta (5)-C5H4C(O)C2H4CO2 C2H5)] reacts with (p-CH3OC6H4)(2)TeO (BMPTO) through oxygen transfer reaction to give mono-(p-CH3OC6H4)(2)Te (BMPT)-substituted clsuter (mu (3)-S)FeCoMo(CO)(7)(MPT) [eta (5)-C5H4C(O)C2H4CO2C2H5] (2), the double tetrahedral cluster [(mu (3)-S)FeCoMo(CO)(8)](2) [eta (5)-C5H4C(O)CH2](2) (3) prepared from (mu (3)-S)FeCo2(CO)(9) and Na-2[Mo(CO)(3)(eta (5)-C5H4C(O)CH2)](2) reacts with BMPTO to afford mono- and bis-BMPT-substituted clusters [(mu (3)-S)FeCoMo(CO)(7)(BMPT)][eta (5)-C5H4C(O)CH2](2)[mu (3)-S)FeCoMo(CO)(8)] (4) and [mu (3)-S)FeCoMo(CO)(7) (BMPT)](2)[eta (5)-C5H4C(O)CH2](2) (5). Similarly, while the double cluster [(mu (3)-S)FeCoMo(CO)(8)](2)[eta (5)-C5H4C(O)CH2](2) (6) reacts with BMPTO to give mono- and bis-BMPT-substituted clusters [(mu (3)-S)FeCoMo(CO)(7)(BMPT)][eta (5)-(CHC)-H-5-C-4(O)CH2](2)[(mu (3)-Se)FeCoMo(CO)(8)] (7) and [(mu (3)-Se)FeCoMo(CO)(7)(BMPT)](2)[eta (5)-C5H4C(O)CH2](2) (8), reaction of [(mu (3)-S)FeCoMo(CO)(8)](2)[(eta (5)-C5H4C2H4)(2)O] (9) with BMPTO affords corresponding mono- and bis-BMPT-substituted clusters [(mu (3)-S)FeCoMo(CO)(7) (BMPT)][(eta (5)-C5H4C2H4)(2)O][(mu (3)-S)FeCoMo(CO)(8)] (10) and [(mu (3)-S)FeCoMo(CO)(7) (BMPT](2)[(eta (5)-C5H4C2H4)(2)O]. 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 (mu (3)-S)FeCoMo(CO)(7)(PPh3)[eta (5)-C5H4C(O)C2H4CO2C2H5] (12), and bis-PPh3-substituted cluster [(mu (3)-S)FeCoMo(CO)(7)(PPh3)](2)[eta (5)-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. (C) 2001 Elsevier Science B.V. All rights reserved.