Rational Syntheses, Structure, and Properties of the First Bismuth(II) Carboxylate

Bismuth(II) trifluoroacetate (1), the first inorganic salt of bismuth in oxidation state +2, has been obtained in its pure, unstabilized form. Several synthetic routes suggested for the isolation of the new compound include (i) mild oxidation of elemental bismuth with some metal trifluoroacetates, e.g., AgI and HgII; (ii) mild reduction of bismuth(III) trifluoroacetate with metals, such as Zn; (iii) comproportionation reaction between Bi and Bi(O2CCF3)3. The last approach gives the title compound 1 in quantitative yield as a sole product. Bismuth(II) trifluoroacetate has been characterized by NMR, IR, and UV−vis spectroscopy as well as by single-crystal X-ray diffraction. Crystallographic study reveals the dinuclear paddle-wheel structure for diamagnetic molecules Bi2(O2CCF3)4. The Bi−Bi bond distances in dimetal units of 1 are averaged to 2.9462(3) Å, and there are no axial intermolecular contacts between these units in the solid state. The compound is volatile and exists in vapor phase up to 220 °C when it disproportionates back to Bi0 and BiIII species, i.e., by the reverse of the synthetic route iii. In contrast, the solution chemistry is quite limited:  the bismuth(II) trifluoroacetate is decomposed by the majority of common solvents, but it can be stabilized by aromatic systems. The dibismuth unit has been shown to be preserved in the latter solvents and can be crystallized out in a form of π-adducts with arenes. Two such adducts, Bi2(O2CCF3)4·(C6H5Me) (2) and Bi2(O2CCF3)4·(1,4-C6H4Me2)2 (3), have been isolated as single crystals and characterized by X-ray diffraction techniques. In the structures of both 2 and 3, the bismuth(II) centers exhibit weak η6-coordination to aromatic rings

Further Studies of the Isomeric 1,2,7- and 1,3,6-Re₂Cl₅(PMe₃)₃ Compounds

New studies of compounds containing Re2Cl5(PMe3)3 molecules have been carried out on products prepared by one-electron oxidation of Re(II)−Re(II) compounds as well as by one-electron reduction of Re(III)−Re(III) species. The action of PhI·Cl2 on Re2Cl4(PMe3)4 in 2:1 mole ratio, in the presence of free PMe3, gives red 1,3,6-/1,2,7-Re2Cl5(PMe3)3 (1) containing two isomers in its unit cell. It was also shown that some additional 1,3,6-Re2Cl5(PMe3)3, isolated as its 1/2CH2Cl2 solvate (2), is always present in the reaction product. The reaction of the quadruply bonded complex [(n-Bu)4N]2Re2Cl8 with PMe3 in propanol at room temperature leads to 1,2,7-Re2Cl5(PMe3)3·(n-Bu)4NCl (3). Heating a dichloromethane solution of compound 3 results in pure 1,2,7-Re2Cl5(PMe3)3. All molecules are characterized by a Re25+ core with a σ2π4δ2δ* bond of order 3.5 and Re−Re distances within the range 2.210−2.227 Å. Crystal data are as follows:  for 1, monoclinic space group P21/c, a = 14.936(5) Å, b = 8.8206(8) Å, c = 34.29(1) Å, β = 90.77(2)°, V = 4517(2) Å3, Z = 8; for 2, monoclinic space group P21/n, a = 8.907(1) Å, b = 16.112(1) Å, c = 16.683(3) Å, β = 94.751(6)°, V = 2385.9(5) Å3, Z = 4; for 3, triclinic space group P1, a = 8.911(2) Å, b = 10.686(2) Å, c = 10.979(3) Å, α = 101.12(2)°, β = 106.82(2)°, γ = 91.29(2)°, V = 978.5(4) Å3, Z = 1

Further Studies of the Isomeric 1,2,7- and 1,3,6-Re₂Cl₅(PMe₃)₃ Compounds

New studies of compounds containing Re2Cl5(PMe3)3 molecules have been carried out on products prepared by one-electron oxidation of Re(II)−Re(II) compounds as well as by one-electron reduction of Re(III)−Re(III) species. The action of PhI·Cl2 on Re2Cl4(PMe3)4 in 2:1 mole ratio, in the presence of free PMe3, gives red 1,3,6-/1,2,7-Re2Cl5(PMe3)3 (1) containing two isomers in its unit cell. It was also shown that some additional 1,3,6-Re2Cl5(PMe3)3, isolated as its 1/2CH2Cl2 solvate (2), is always present in the reaction product. The reaction of the quadruply bonded complex [(n-Bu)4N]2Re2Cl8 with PMe3 in propanol at room temperature leads to 1,2,7-Re2Cl5(PMe3)3·(n-Bu)4NCl (3). Heating a dichloromethane solution of compound 3 results in pure 1,2,7-Re2Cl5(PMe3)3. All molecules are characterized by a Re25+ core with a σ2π4δ2δ* bond of order 3.5 and Re−Re distances within the range 2.210−2.227 Å. Crystal data are as follows:  for 1, monoclinic space group P21/c, a = 14.936(5) Å, b = 8.8206(8) Å, c = 34.29(1) Å, β = 90.77(2)°, V = 4517(2) Å3, Z = 8; for 2, monoclinic space group P21/n, a = 8.907(1) Å, b = 16.112(1) Å, c = 16.683(3) Å, β = 94.751(6)°, V = 2385.9(5) Å3, Z = 4; for 3, triclinic space group P1, a = 8.911(2) Å, b = 10.686(2) Å, c = 10.979(3) Å, α = 101.12(2)°, β = 106.82(2)°, γ = 91.29(2)°, V = 978.5(4) Å3, Z = 1

Tuning the Properties at Heterobimetallic Core: Mixed-Ligand Bismuth−Rhodium Paddlewheel Carboxylates

Mixed-ligand heterometallic compounds [BiRh(O2CCF3)4-x(O2CR)x] (R = But, x = 2 (cis); R = Me, Bui, x = 1) have been obtained by gas-phase reactions of bismuth(II) trifluoroacetate with the corresponding rhodium(II) carboxylate. This synthetic approach was found to be very effective for tuning the properties and introduction of chiral ligands at a heterobimetallic core

Heterometallic Bismuth-Transition Metal Homoleptic β-Diketonates

Bismuth(III) hexafluoroacetylacetonate reacts readily with the first row transition-metal species to produce trinuclear heterobimetallic coordination complexes Bi2M(β-diketonate)8 (M = Mn, Fe, Co, Ni, Cu, Zn). This unique, general approach may offer new possibilities for developing single-source molecular precursors for advance oxide materials

Heterometallic Bismuth-Transition Metal Homoleptic β-Diketonates

Bismuth(III) hexafluoroacetylacetonate reacts readily with the first row transition-metal species to produce trinuclear heterobimetallic coordination complexes Bi2M(β-diketonate)8 (M = Mn, Fe, Co, Ni, Cu, Zn). This unique, general approach may offer new possibilities for developing single-source molecular precursors for advance oxide materials

Tuning the Properties at Heterobimetallic Core: Mixed-Ligand Bismuth−Rhodium Paddlewheel Carboxylates

Mixed-ligand heterometallic compounds [BiRh(O2CCF3)4-x(O2CR)x] (R = But, x = 2 (cis); R = Me, Bui, x = 1) have been obtained by gas-phase reactions of bismuth(II) trifluoroacetate with the corresponding rhodium(II) carboxylate. This synthetic approach was found to be very effective for tuning the properties and introduction of chiral ligands at a heterobimetallic core

Heterometallic Bismuth-Transition Metal Homoleptic β-Diketonates

Bismuth(III) hexafluoroacetylacetonate reacts readily with the first row transition-metal species to produce trinuclear heterobimetallic coordination complexes Bi2M(β-diketonate)8 (M = Mn, Fe, Co, Ni, Cu, Zn). This unique, general approach may offer new possibilities for developing single-source molecular precursors for advance oxide materials

Heterometallic Bismuth-Transition Metal Homoleptic β-Diketonates

Bismuth(III) hexafluoroacetylacetonate reacts readily with the first row transition-metal species to produce trinuclear heterobimetallic coordination complexes Bi2M(β-diketonate)8 (M = Mn, Fe, Co, Ni, Cu, Zn). This unique, general approach may offer new possibilities for developing single-source molecular precursors for advance oxide materials

Heterometallic Bismuth-Transition Metal Homoleptic β-Diketonates

Bismuth(III) hexafluoroacetylacetonate reacts readily with the first row transition-metal species to produce trinuclear heterobimetallic coordination complexes Bi2M(β-diketonate)8 (M = Mn, Fe, Co, Ni, Cu, Zn). This unique, general approach may offer new possibilities for developing single-source molecular precursors for advance oxide materials