Reactions of the dirhenium and dimanganese complexes [Re2(CO)10−x(NCMe)x] (x = 0, 1, 2) and [Mn2(CO)10] with tri(2-thienyl)phosphine in different conditions are studied. A variety of mono-and dinuclear complexes are obtained from these reactions by C-P bond cleavage of the tri(2thienyl)phosphine ligand.
The reactivity of group 7 metal dinuclear carbonyl complexes [M(2)(CO)(6)(mu-SN(2)C(4)H(5))(2)] (1, M = Re; 2, M = Mn) toward group 8 metal trinuclear carbonyl clusters were examined. Reactions of 1 and 2 with [Os(3)(CO)(10)(NCMe)(2)] in refluxing benzene furnished the tetranuclear mixed-metal clusters [Os(3)Re(CO)(13)(mu(3)-SN(2)C(4)H(5))] (3) and [Os(3)Mn(CO)(13)(mu(3)-SN(2)C(4)H(5))] (4), respectively. Similar treatment of 1 and 2 with Ru(3)(CO)(12) yielded the ruthenium analogs [Ru(3)Re(CO)(13)(mu(3)-SN(2)C(4)H(5))] (5), and [Ru(3)Mn(CO)(13)(mu(3)-SN(2)C(4)H(5))] (6), but in the case of 2 a secondary product [Mn(3)(CO)(10)(mu-Cl)(mu(3)-SN(2)C(4)H(5))(2)] (7) was also formed. Compounds have a butterfly core of four metal atoms with the M (Mn or Re) at a wingtip of the butterfly and containing a noncrystallographic mirror plane of symmetry. This result provides a potential method for the synthesis of a series of new group 7/8 mixed metal complexes containing a bifunctional heterocyclic ligand. Compound 7 is a unique example of a 54-electron trimanganese complex having bridging 2-mercapto-1-methylimidazolate and chloride ligands. Interestingly, the reaction of 1 with Fe(3)(CO)(12) at 70-75 degrees C furnished the tri- and dirhenium complexes [Re(3)(CO)(10)(mu-H)(mu(3)-SN(2)C(4)H(5))(2)] (8) and [Re(2)(CO)(6)(N(2)C(4)H(5))(mu-SN(2)C(4)H(5))(2)] (9), respectively instead of the expected formation of the mixed-metal clusters. The former is an interesting example of a 52-electron trirhenium-hydridic complex containing bridging 2-mercapto-1-methylimidazolate ligand, while the latter can be viewed as a 1-methylimidazole adduct of 1 . No mixed Fe-Re complexes were produced in this reaction. The molecular structures of the new compounds and were established by single-crystal X-ray diffraction analyses and the DFT studies of compounds , and are reported.
Reaction of electron-deficient [Os3(CO)8{μ3-Ph2PCH2P(Ph)C6H4}(μ-H)] (2) with Ph3SnH at ambient temperature yields the bimetallic osmium−tin dihydride complexes [Os3(CO)8{μ3-Ph2PCH2P(Ph)C6H4}(SnPh3)(μ-H)2] (3) and [Os3(CO)8(μ-dppm)(SnPh3)2(μ-H)2] (4) via oxidative-addition of one and two Sn−H bonds, respectively, the latter having SnPh3 ligands bound to adjacent osmium atoms. Cluster 3 converts to 4 via oxidative-addition of a further Sn−H bond followed by reductive-elimination of the orthometalated diphosphine. Heating 4 at 128 °C affords isomeric 5, in which both the SnPh3 ligands are bound to the same metal atom, and 5 is also formed from 2 and excess Ph3SnH at 128 °C. Reaction of [Os3(CO)10(μ-dppm)] (1), the saturated counterpart of 2, with Ph3SnH at 110 °C affords [Os3(CO)9(μ-dppm)(SnPh3)(μ-H)] (6), via oxidative-addition of one Sn−H bond, and this converts to 3 upon further heating via loss of one CO followed by orthometallation of the diphosphine. Treatment of 3 with hydrogen (1 atm) at 110 °C gives both the unsaturated dihydride [Os3(CO)7{μ3-Ph2PCH2P(Ph)C6H4}(SnPh3)(μ-H)2] (7) and the electron-precise trihydride [Os3(CO)8(μ-dppm)(SnPh3)(μ-H)3] (8). Thermolysis of 8 at 110 °C gives 7, while heating 3 in refluxing octane yields, after recrystallization from dichloromethane, the unsaturated cluster [Os3(CO)7{μ3-Ph2PCH2P(Ph)C6H4}(SnPh2Cl)(μ-H)2] (9), whereby the coordinated SnPh3 is transformed into a SnPh2Cl group probably via Sn−Ph bond cleavage and chloride addition to the resulting μ-SnPh2 group. The crystal structures of six of these new osmium−tin clusters have been carried out, allowing a detailed analysis of the relative orientations of metal atoms.
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