The First Clusters with a Y‐Shaped Arrangement of Ligands at Three‐Coordinate RhI Atoms in the Solid State: [M1M2{μ‐P(C6H11)2}(CO)8Rh(PPh3)] (M1, M2 = Mn, Re)

The reaction of Mn2(CO)7(μ-S2), 2, with CpCo(CO)2 and Cp*Rh(CO)2 (Cp* = C5Me5) yielded the new complexes CpCoMn2(CO)6(μ3-S)2, 3, and Cp*RhMn2(CO)6(μ3-S)2, 4, in 79% and 38% yields, respectively. The reaction of 2 with CpCo(CO)(PPh3) yielded 3, CpCoMn2(CO)5(PPh3)(μ3-S)2, 5 (a phosphine derivative of 3), and Mn2(CO)6(PPh3)(μ-S2), 6 (a phosphine derivative of 2). Compound 5 was also obtained in 88% yield from the reaction of 3 with PPh3. All new products were characterized crystallographically. Compounds 3−5 are structurally similar and consist of a triangular Mn2M cluster with triply bridging sulfido ligands on each side of the Mn2M plane. Compound 6 contains an asymmetrical semibridging carbonyl ligand that is most strongly associated with the phosphine-substituted manganese atom.

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Directed Synthesis of the Triangular Mixed-Metal Cluster H₂RhRe₂Cp*(CO)₉: Ligand Fluxionality and Facile Cluster Fragmentation in the Presence of CO, Halogenated Solvents, and Thiols

Huang

Watson

Carrano

et al. 2009

Organometallics

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The reaction of H2Re2(CO)8 (1) with Cp*Rh(CO)2 (2) in refluxing hexane affords the mixed-metal clusters H2RhRe2Cp*(CO)9 (4, major product), HRh2ReCp*2(CO)6 (5), and HRhRe3Cp*(CO)14 (6). 4 and 5 are electron-precise 48e clusters and display triangular metallic cores, while 6 contains 64 valence electrons and exhibits a spiked-triangular core having a pendant Re(CO)5 moiety. Heating 1 with Cp*2Rh2(CO)2 (3) gives 4 and 5 as the principal products, in addition to H2Rh2Re2Cp*2(CO)8 (7) in low yield. Cluster 7 possesses 60e and contains a tetrametallic core with two face-capping CO and hydride groups. Heating 4 under CO leads to cluster fragmentation and formation of Re2(CO)10 and 2 in essentially quantitative yield, as assessed by IR spectroscopy. The kinetics for the fragmentation of 4 in toluene under CO have been investigated over the temperature range 325−349 K by UV−vis spectroscopy. On the basis of the first-order rate constants and the Eyring activation parameters (ΔH ⧧ = 25.0(8) kcal/mol; ΔS ⧧ = −2.6(3) eu), a rate-limiting step involving a polyhedral opening of 4 is supported. 4 is thermally and photochemically sensitive, and reactions conducted in the presence of chlorinated solvents furnish the face-shared bioctahedral compound Cp*Rh(μ-Cl)3Re(CO)3 (8). Heating 4 and H2S in benzene at ca. 60 °C furnishes the 48e triangular cluster S2Rh3Cp*(CO)4 (9), which contains two Rh(CO)2 moieties and two face-capping sulfide groups. The reaction of 4 with p-methylbenzenethiol gives the sulfido-bridged dimer Cp*Rh(μ-SC6H4Me-p)3Re(CO)3 (11). The dinuclear compounds Cp*Rh(μ-Cl)(μ-SC6H4Me-p)2Re(CO)3 (10) and 11 are formed when 8 is allowed to react with p-methylbenzenethiol. Treatment of 8 and 10 with excess p-methylbenzenethiol yields 11 at elevated temperature in toluene. Compounds 4−11 have been isolated and fully characterized by IR and NMR spectroscopy and by X-ray crystallography. The reactivity displayed by 4 is contrasted with that of the known indenyl-substituted cluster H2Re2Ir(η5-ind)(CO)9 prepared earlier by Shapley and co-workers.

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The First Clusters with a Y‐Shaped Arrangement of Ligands at Three‐Coordinate Rh^I Atoms in the Solid State: [M¹M²{μ‐P(C₆H₁₁)₂}(CO)₈Rh(PPh₃)] (M¹, M² = Mn, Re)

Cited by 5 publications

References 19 publications

Reactions of SmI2(THF)x with [Cp′Mo(CO)3]2Hg(Cp′  C5H5− or C5Me5−): crystal and molecular structures of [(THF)4I2Sm(μ-OC)Mo(CO)2(C5H5)] and [(C5Me5)Mo(CO)3]2

Reactions of SmI2(THF)x with [Cp′Mo(CO)3]2Hg(Cp′  C5H5− or C5Me5−): crystal and molecular structures of [(THF)4I2Sm(μ-OC)Mo(CO)2(C5H5)] and [(C5Me5)Mo(CO)3]2

Insertion of Cyclopentadienylmetal Groups into the S−S Bond of Mn₂(CO)₇(μ-S₂)

Directed Synthesis of the Triangular Mixed-Metal Cluster H₂RhRe₂Cp*(CO)₉: Ligand Fluxionality and Facile Cluster Fragmentation in the Presence of CO, Halogenated Solvents, and Thiols

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The First Clusters with a Y‐Shaped Arrangement of Ligands at Three‐Coordinate RhI Atoms in the Solid State: [M1M2{μ‐P(C6H11)2}(CO)8Rh(PPh3)] (M1, M2 = Mn, Re)

Cited by 5 publications

References 19 publications

Reactions of SmI2(THF)x with [Cp′Mo(CO)3]2Hg(Cp′  C5H5− or C5Me5−): crystal and molecular structures of [(THF)4I2Sm(μ-OC)Mo(CO)2(C5H5)] and [(C5Me5)Mo(CO)3]2

Reactions of SmI2(THF)x with [Cp′Mo(CO)3]2Hg(Cp′  C5H5− or C5Me5−): crystal and molecular structures of [(THF)4I2Sm(μ-OC)Mo(CO)2(C5H5)] and [(C5Me5)Mo(CO)3]2

Insertion of Cyclopentadienylmetal Groups into the S−S Bond of Mn2(CO)7(μ-S2)

Directed Synthesis of the Triangular Mixed-Metal Cluster H2RhRe2Cp*(CO)9: Ligand Fluxionality and Facile Cluster Fragmentation in the Presence of CO, Halogenated Solvents, and Thiols

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The First Clusters with a Y‐Shaped Arrangement of Ligands at Three‐Coordinate Rh^I Atoms in the Solid State: [M¹M²{μ‐P(C₆H₁₁)₂}(CO)₈Rh(PPh₃)] (M¹, M² = Mn, Re)

Insertion of Cyclopentadienylmetal Groups into the S−S Bond of Mn₂(CO)₇(μ-S₂)

Directed Synthesis of the Triangular Mixed-Metal Cluster H₂RhRe₂Cp*(CO)₉: Ligand Fluxionality and Facile Cluster Fragmentation in the Presence of CO, Halogenated Solvents, and Thiols