Er-Run Ding

The reaction of (μ3-CCO2R)Co2M(CO)8L (M = Co, Mo, W; L = CO, MeCp; R = Me, Et) with Na2[Fe(CO)4]. X-ray crystal structure analysis of (EtO2CCCCO2Et)Co4(CO)10 and (MeO2CCCCO2Me)FeCo2(CO)9

Abstract The reactions of clusters [(μ 3 - CCO 2 Et ) Co 2 M ( CO ) 8 ( MeCp )][ M = Mo ( 2 a ), W ( 2 b )] , derived from the reactions of (μ3-CCO2Et)Co3(CO)9 with Na[M(CO)3(MeCp)], with Na2[Fe(CO)4] in THF at reflux not only gave the expected metal fragment exchange products [(μ 3 - CCO 2 Et ) FeCoM(CO) 8 ( MeCp ) H ][ M = Mo ( 3 a ), W ( 3 b )] , but also gave the unexpected compounds [(μ 3 - CCO ) FeCoM(CO) 8 ( MeCp )][ M = Mo ( 4 a ), W ( 4 b ) . It is suggested that the formation of two kinds of compounds resulted from two competitive reactions of the intermediates [(μ3-CCO2Et)FeCoM(CO)8(MeCp)]− with acidic treatment: the one is the protonic reaction of the intermediate giving the clusters 3a and 3b; the other is the intermolecular nucleophilic substitution reaction of the intermediate by the catalysis of H+, giving the clusters 4a and 4b. Under the different reaction temperature and molar ratio of the starting materials, the reactions of (μ 3 - CCO 2 R ) Co 3 ( CO ) 9 [ R = Me ( 1 1 ), Et ( 1 b )] [ R = Me ( 6 a ) , Et (6b)] abd (RO2CCCCO2R)FeCo2(CO)9[R = Me (7a), Et (7b)] besides the expected exchange products (μ 3 - CCO 2 R ) FeCo 2 ( CO ) 9 H [ R = Me ( 5 a ), Et ( 5 b )] . This is the first example that the reaction of 6a and 6b with Na2[Fe(CO)4] could produce the clusters 7a and 7b. The clusters (EtO2CCCCO2Et)Co4(CO)10 and (RO2CCCCO2R)FeCo2(CO)9 were determined structurally by X-ray diffraction.

Synthesis and expansion reaction of ferrocenylacetylene dimetal carbonyl compounds. The molecular structures of μ -FcCCHCoMo(CO) 5 Cp and μ 3 -FcCHCFeCo 2 (CO) 9

Two ferrocenylacetylene dimetal carbonyl clusters μ -FcCCHCo(CO) 3 M(CO) 2 Cp ( 2 , M=Mo; 3 , M=W) were obtained from the reactions of the precursor μ -FcCCHCo 2 (CO) 6 1 with metal exchange reagents NaM(CO) 3 Cp in THF under reflux. The dimetal compounds 1 , 2 , and 3 can further react with Fe 2 (CO) 9 in the presence of benzylideneacetone (BDA) to give the corresponding μ 3 -ferrocenylvinylidene bridged trimetal clusters μ 3 -FcCHCFeCo 2 (CO) 9 4 and μ 3 -FcCHCFeCoM(CO) 8 Cp ( 5 , M=Mo; 6 , M=W), respectively, probably through the formation of the intermediate (BDA)Fe(CO) 3 which acts as an Fe(CO) 3 transfer-reagent. The new compounds 2 – 6 were characterized by C/H analysis, IR and 1 H-NMR spectrocopies. The molecular structures of 2 and 4 were determined by X-ray structural analysis. 2 is triclinic with space group P 1 (#2), a =8.733(2) A, b= 14.870(3) A, c =8.200(2) A, α =92.77(2)°, β =101.78(2)°, γ =78.41(2)°, V =1021.2(4) A 3 , and Z =2; final R= 0.025, R w =0.034 for 2988 reflections. Cluster 4 is orthorhombic with space group P 2 1 2 1 2 1 (#19), a =12.186(5) A, b= 14.870(5) A, c =7.800(6) A, V =2340(2) A 3 and Z =4; final R= 0.062, R w = 0.065 for 2401 reflections.

Synthesis, characterization and reaction of the cluster complexes containing tetrahedral core MRuCoSe. The single crystal X-ray structures of the clusters RuCoMo(CO)8(μ3-Se)C5H4C(O)R [R=CH3, C6H4C(O)OCH3]

Abstract Several chiral cluster derivatives RuCoMo(μ3-Se)(CO)8C5H4C(O)R [R=H 2, CH3 3, C6H5 4, C6H4C(O)OCH3 5] were synthesized by the thermal reaction of the precursor (μ3-Se)RuCo2(CO)9 1 with the functionally substituted cyclopentadienyl tricarbonyl metal complex anions [Mo(CO)3(η5-C5H4)C(O)R]− without using benzophenone ketyl as initiator. Similarly, the reaction of the novel type of dianions −Mo(CO)3[(η5-C5H4)C(O)C6H4C(O)(η5-C5H4)](CO)3Mo− with two molecules of cluster 1 gave a terephthaloyl(biscyclopentadienyl) bridged cluster complex (μ3-Se)RuCoMo(CO)8(η5-C5H4)C(O)C6H4C(O)(η5-C5H4)RuCoMo(CO)8(μ3-Se) 6. The cluster 3 reacted with NaBH4 in MeOH to give the secondary alcohol cluster RuCoMo(μ3-Se) (CO)8C5H4CH(OH)CH3 7. Cluster 3 reacted with Na2Fe(CO)4 in THF under reflux followed by acidic treatment with 40% H3PO4 to yield the new cluster HRuFeMo(μ3-Se)(CO)8C5H4C(O)CH3 8. Cluster 3 and 5 have been solved by single-crystal X-ray diffraction. Crystal data for cluster 3: orthorhombic, space group Pbca, a=26.387(3) A, b=18.273(2) A, c=15.963(2) A, V=7696(2) A3, Z=16 and R=0.023, wR=0.027. Crystal data for cluster 5: triclinic, space group P1, a=8.200(2) A, b=19.631(7) A, c=7.997(2) A, α=92.50(2)°, β=108.66(2)°, γ=88.97(2)°, V=1218.5(6) A3, Z=2 and R=0.054, wR=0.077.

Synthesis and reduction of [RuCoMo (μ3-S)(CO)8(RC5H4)] [R HC(O) (2), CH3C(O) (3), C6H5(O) (4), CH3OC(O)C6H4C(O) (5)] heterometal clusters and structure of [RuCoMo (μ3-S)(CO)8C5H4C(O)C6H4C(O)OCH3]

Abstract The heterometal clusters [SRuCoMo(CO)8C5H4R][R  HC(O) (2), CH3C(O) (3), C6H5C(O) (4), CH3OC(O)C6H4C(O) (5)] were synthesized by refluxing a solution of the cluster 1 [RuCo2(μ3-S)(CO)9] monoanions[η5-RC5H4(CO)3Mo] [R  HC(O), CH3C(O), C6H5C(O), CH3OC(O)C6H4C(O)]. Cluster 3 reacted with NaBH4 in MeOH giving the secondary alcohol cluster RuCoMo(μ3-S)(CO)8 [η5-C5H4CH(OH)CH3]. All clusters were characterizec by C, H analysis, IR and 1H NMR. Some were characterized by MS and 13C NMR. The results showed that the metal fragment Co(CO)3 in RuCo(μ3-S)(CO)9 could be exchanged by Mo(CO)2(C5H4R). Cluster 5 has been structurally determined by single-crystal X-ray diffraction.

Synthesis and characterization of chiral (μ3-S)FeCoM(CO)8(RCp) [M = Mo, W; R = C6H5C(O), CH3OC(O)C6H4C(O)] clusters and the crystal structures of (μ3-S)FeCoMo(CO)8[CH3OC(O)C6H4C(O)Cp] and (μ3-S)FeCoW(CO)8[CH3OC(O)C6H4C(O)Cp]

Abstract Several chiral cluster derivatives [(μ3-S)FeCoM(CO)8(RCp)] [M = Mo, R = C6H5C(O) (2); M = Mo, R = CH3OC(O)C6H4C(O) (3); M = W, R = C6H6C(O) (4), M = W, R = CH3OC(O)C6H4C(O) (5)] were synthesized by the thermal reaction of (μ3-S)FeCo2(CO)9 (1) with the functionally substituted cyclopentadienyl tricarbonyl metal complex anions [M(CO)3RC(O)Cp]− without using benzophenone ketyl to initiate the reaction. The cluster (2) reacted with NaBH4 in MeOH gave the secondary alcohol cluster (μ3-S) FeCoMo(CO)8C6H5CH(OH)Cp. These clusters were characterized by C/H analysis, IR, 1H NMR, 13C NMR and MS. The results showed that the metal fragment Co(CO)3 in (μ3-S)FeCo2(CO)9 could be exchanged by M(CO)2RC(O)Cp. The structures of (μ3-S)FeCoMo[CH3O(O)C6H4C(O)Cp] (4) and (μ3-S)FeCoW(CO)8 [CH3OC(O)C6H4C(O)Cp] (5) were determined by single crystal X-ray diffraction.

Study on the reactivity of RuCo2(μ3–S)(CO)9: synthesis and characterization of the cluster complexes containing the tetrahedral core MRuCoS (MMo, W) and the two tetrahedral core MRuCoS clusters

New clusters MRuCo(CO) 8 ( μ 3 -S)[ η 5 -C 5 H 4 C(O)CH 3 ] (MMo 2 , W 3 ) and [MRuCo(CO) 8 ( μ 3 -S)] 2 [ η 5 -C 5 H 4 C(O)C 6 H 4 C(O)C 5 H 4 - η 5 ][MMo 4 , W 5 ] have been isolated from the reaction of RuCo 2 ( μ 3 -S)(CO) 9 1 with [ η 5 -C 5 H 4 C(O)CH 3 (CO) 3 M] − (MMo, W) and − [M(CO) 3 { η 5 -C 5 H 4 C(O)C 6 H 4 C(O)C 5 H 4 - η 5 }(CO) 3 M] − [MMo, W], respectively. Clusters 2 and 5 have been established by single crystal X-ray diffraction methods. The crystals of cluster 2 are orthorhombic with space group Pbca , a =26.229(7), b =18.200(3), c =15.929(4) A, V =7604(6) A 3 and Z =18; final R= 0.033, R w =0.045. The crystals of cluster 5 are triclinic space group P 1, a =12.688(4), b =20.290(7), c =9.429(3) A, α =99.78(3), β =90.64(2), γ =78.28(3)°, V =2341(1) A 3 and Z =4; final R =0.042, R w =0.063.

Reaction of (μ3-Se)RuCo2(CO)9: Synthesis and Crystal Structure of the Chiral Skeleton Clusters (μ3-Se)RuCoM(CO)8[C5H3(CH3)(COCH3)] (M=Mo, W)

Abstract The reaction of (μ3-Se)RuCo2(CO)9 (1) with the functionally substituted cyclopentadienyl tricarbonyl metal anions M(CO)3C5H3[(CH3)(COCH3)] (M = Mo, W) in reluxing THF gave new chiral skeleton clusters (μ3-Se)RuCoM(CO)8[C5H3(CH3)(COCH3)] [M = Mo (4), W (5)]. X-ray data for (4) show that it is orthorhombic, space group Pbca, a = 13.712(7)A, b = 16.451(8)A, c = 18.44(1)A, V. = 4158(6)A3, Z. = 8, Dc = 2.172g/cm3, R. = 0.073 and Rw = 0.087. All of the clusters were further characterized by their C/H analyses, IR, 1H NMR, 13C NMR and MS FAB spectra.

Reaction of dipropargyl phthalate with Co2(CO)8 and Mo2Cp2(CO)4 gives the di or tetranuclear clusters. The crystal structure of [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6]2 and [o-(HC2CH2OCO)C6H4(CO2CH2C2H-μ)][Mo2Cp2(CO)4]–CH2Cl2

Abstract The reaction of dipropargyl phthalate with Co2(CO)8 in benzene at room temperature gave a new cluster [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6]2 1, which reacts with the cyclopentadienyl tricarbonyl molybdenum anion [Mo(CO)3Cp]− to form the tetranuclear clusters [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6][CoMoCp(CO)5] 2 and [C6H4-1,2-(CO2CH2C2H-μ)2] [CoMoCp(CO)5]2 3, respectively. The reaction of Mo2Cp2(CO)4 with dipropargyl phthalate gave rise to the formation of the dinuclear cluster [o-(HC2CH2OCO)C6H4(CO2CH2C2H-μ)][Mo2Cp2(CO)4] 4 and tetranuclear cluster [C6H4-1,2-(CO2CH2C2H-μ)2] [Mo2Cp2(CO)4]2 5, respectively. The cluster 4 reacted with Co2(CO)8 to produce the tetranuclear cluster [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6] [Mo2Cp2(CO)4] 6. These clusters were characterized by C/H analyses, IR and 1H NMR. The structure of [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6]2 1 and [o-(HC2CH2OCO)C6H4 (CO2CH2C2H-μ)][Mo2Cp2(CO)4]-CH2Cl2 4·CH2Cl2 were determined by single crystal X-ray diffraction methods.

Syntheses and Reactions of Dimolybdenum Alkyne Compounds Containing Functionally Substituted Ligands. The Crystal Structure of [Co2Mo2(μ4-CHCH)(μ-CO)4(CO)4-(η5-C5H4C(O)Me)2]

Abstract Three dimolybdenum alkyne complexes containing functionally substituted ligands [Mo2(μ-CHCH)(CO)4(η5‒C5H4C(O)R)2] [R ˭ OEt, (1a); R ˭ Me, (1b); R ˭ Ph, (1c)] were synthesized by reactions of acetylene with in situ generated metal-metal triply bonded complexes [Mo(CO)2(η5‒C5H4C(O)R)]2 (R ˭ OEt, Me, Ph). Further reaction of (1a), (1b) or (1c) with Co2(CO)8 in refluxing toluene gave another three new butterfly compounds [Co2Mo2-(μ4-CHCH)(μ-CO)4(CO)4(η5-C5H4C(O)R)2] [R ˭ OEt, (2a); R ˭ Me, (2b); R ˭ Ph, (2c)]. The resulting compounds were characterized by elemental analyses, IR, 1H NMR and MS. The crystal structure of (2b) was determined by single-crystal X-ray analysis. The results indicate that the existence of functional groups on the cyclopentadienyl ring has an influence on the reactivity of this type of complex.

Synthesis and Reaction of New Metal Cluster Complexes Containing a Wrucose Core

Abstract Several chiral cluster derivatives, RuCoW(μ3Se)(CO)8{η5-C5H4C(O)R} [R = H (2), CH3 (3), C6H5 (4), C6H5C(O)OCH3 (5)], were” synthesized by reaction of the precursor (μ3-Se)RuCo2(CO)t) (1) with the functionally substituted cyclopentadienyl tricarbonyl metal complex anions [W(CO)3{η5-C5H4C(O)R}]−without using benzophenone ketyl. A new double-tetrahedral cluster compound, p-[(μ3-Se)(CO)8RuCoW(μ5-C5H4C(O))]2C6H4 (6), was obtained by treating (1) with a metal exchange reagent, Na2[W(CO)3(η5-C5H4)C(O)C6H4C(O)(η5-C5H4)}(CO)3WJ. Cluster (3) reacted with NaBH4 in MeOH to give the secondary alcohol cluster RuCoW(μ3-Se)(CO)8{η5-C5H4CH(OH)CH3} (7). The cluster (3) reacted with Na2Fe(CO)4 in refluxing THF followed by the treatment of 40% H3PO4 to yield the new cluster HRuFeW(μrSe)(CO)8{η5-C5H4C(O)CH3} (8). The structure of cluster (3) has been determined by single-crystal X-ray diffraction. Crystal data for cluster (3) give an orthorhombic space group Pbca, a - 26.326(4) A, b = 18.231(4) A, c = 15.956(3) A, V ...