Yuan-Qi Yin

Synthesis and X-ray crystal structure of the chiral trimetal carbonyl clusters (μ3-CPh)FeCoMo(CO)8(RCOCp)H (R = H, CH3 or C2H5O) derived from the clusters (μ3-CPh)Co2Mo(CO)8(RCOCp)

Abstract Three μ3-phenylmethylidyne trimetal carbonyl clusters (μ3-CPh)Co2Mo(CO)8(RCOCp) (2, R = H; 3; R = CH3; 4, R = C2H5O) have been obtained from the reaction of the precursor (μ3-CPh)Co3(CO3(CO)9 with the metal exchange reagents NaM(CO)3(RCOCp) in THF under reflux. Reaction of (μ3-CPh)CO2Mo (CO)8(RCOCp) clusters with Na2[Fe(CO)4] in THF under reflux followed by acidic treatment with 40% H3PO4 yielded three new chiral clusters (μ3-CPh)FeCoMo(CO)8(RCOCp)H (5, R = H; 6, CH3; 7, C2H5O). Experimental results indicate that the electron-withdrawing groups RCO on cyclopentadienyl reduce the activity of the metal exchange reagents NaMo(CO)3(RCOCp) and that the rate of the above reaction increases with increasing temperature. Cobalt carbonyl units Co(CO)3 in the clusters PhCCo3(CO)9 and PhCCo2Mo(CO)8(RCOCp) may be exchanged by organometallic fragments Mo(CO)2(RCOCp) and Fe(CO)3, respectively. Clusters 5–7 were characterized by C/H analysis and IR and 1H NMR spectroscopies and the crystal structures of 4 and 7 were determined. Cluster 4 is monoclinic with space group P2 1 /c, a = 11.356(2) A , b = 14.030(2) A , c = 16.076(3) A , β = 107.19(1)°, V = 2446.8(7) A 3 and Z = 4; final R = 0.048 and Rw = 0.057 for 4751 reflections. Cluster 7 is monoclinic with space group P2 1 /c, a = 12.167(5) A , b = 14.032(7) A , c = 15.159(7) A , β = 105.21(3)°, V = 2497(2) A 3 and Z = 4; final R = 0.0468 and Rw = 0.0410 for 3959 reflections.

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.

Synthesis, characterization and reactions of cluster complexes containing SeRuCoM (M=Mo or W) core and a functionally substituted cyclopentadienyl ligand

Reactions of monoanions {M(CO) 3 [η 5 -C 5 H 4 C(O)CH 2 CH 2 CO 2 Me]} − with RuCo 2 (CO) 9 (μ 3 -Se) in THF at 60°C gave two new cluster derivatives (μ 3 -Se)CoMRu(CO) 8 [η 5 -C 5 H 4 C(O)CH 2 CH 2 CO 2 Me] (M=Mo 1 , M=W 2 ). Similarly, reactions of dianions − {M(CO) 3 [(η 5 -C 5 H 4 )C(O)CH 2 CH 2 C(O)(η 5 -C 5 H 4 )](CO) 3 M} − with two molecules of RuCo 2 (CO) 9 (μ 3 -Se) gave 1,4-succinoyl(biscyclopentadienyl)-bridged double cluster complexes (μ 3 -Se)CoMRu(CO) 8 [(η 5 -C 5 H 4 )C(O)CH 2 CH 2 C(O)(η 5 -C 5 H 4 )]CoMRu(CO) 8 (μ 3 -Se) (M=Mo 3 , M=W 4 ). Treatment of cluster (μ 3 -Se)CoMoRu(CO) 8 [(η 5 -C 5 H 4 )C(O)Me] with ammine derivatives 2,4-dinitrophenylhydrazine, NH 2 NHC(S)NH 2 , (−)-5-(α-phenyl)semioxamazide and l -(+)-menthydrazide, respectively, at room temperature produced four new hydrazone cluster derivatives (μ 3 -Se)CoMoRu(CO) 8 [η 5 -C 5 H 4 C(NR)Me] (R=NHC 6 H 3 -2,4-(NO 2 ) 2 5 , R=NHC(S)NH 2 6 , R=NHC(O)C(O)NHCH(Me)(C 6 H 5 ) 7 , R=NHCO 2 -menthyl 8 ). However, cluster 1 can only react with 2,4-dinitrophenylhydrazine to give the formation of cluster (μ 3 -Se)CoMoRu(CO) 8 [η 5 -C 5 H 4 C(NR)CH 2 CH 2 CO 2 Me] (R=NHC 6 H 3 -2,4-(NO 2 ) 2 9 ) under similar condition. Although, two kinds of optically active groups have been introduced into cluster (μ 3 -Se)CoMoRu(CO) 8 [(η 5 -C 5 H 4 )C(O)Me], the mixture of diastereoisomers could not be separated by silica gel chromatography. The 13 C-NMR spectra showed the presence of a pair of diastereoisomers.

Synthesis, characterization and crystal structure of hetero-metal clusters RCCo2M(CO)8(CH3Cp) and RCCoM2(CO)7(CH3Cp)2

Abstract Six hetero-metal clusters RCCo 2 M(CO) 8 Cp′ and RCCoM 2 (CO) 7 Cp′ 2 (R = Ph, C 2 H 5 O 2 C; M = Mo, W; Cp′ = CH 3 Cp) were synthesized by refluxing a solution of the clusters RCCo 3 (CO) 9 and NaM(CO) 3 Cp′ in THF through metal exchange reactions, in which the metal unit Co(CO) 3 in the RCCo 3 (CO) 9 cluster was exchanged by M(CO) 2 Cp′. The clusters were characterized by elemental analysis, IR and 1 H NMR along with the crystal structure of [C 2 H 5 O 2 CCCoMo 2 (CO) 7 Cp′ 2 ].

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.

Preparation and x-ray crystal structure of a mixed-metal cluster (η5-CH3C5H4)Mo(μ3-NH)(μ2-NO) (μ2-CO)Fe2(CO)6

Abstract The cluster (η5-CH3C5H4)Mo(μ3-NH)(μ2-NO)(μ2-CO)Fe2(CO)6 was synthesized by the reaction of (η5-CH3C5H4)Mo(CO)3Cl with Na[Fe(CO)3NO], and its crystal structure has been determined by X-ray diffraction. The cluster is a trinuclear complex with a face-bridging NH group which was converted from NO in the reaction.