Xue-Nian Chen

Preparation and characterization of Mo2C2, Co2Mo2C2 clusters containing functionally substituted cyclopentadienyl ligands. The crystal structures of [Mo2(μ-C2HPh)(CO)4(η5-C5H4C(O)Me)2] and [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2]

Through reactions of phenylacetylene with in situ generated metal–metal triply bonded complexes [Mo(CO) 2 (η 5 -C 5 H 4 C(O)R)] 2 (RMe, OEt, Ph), three new μ-alkyne bridged molybdenum compounds containing functionally substituted cyclopentadienyl ligands [Mo 2 (μ-C 2 HPh)(CO) 4 (η 5 -C 5 H 4 C(O)R) 2 ] (RMe, 1a ; ROEt, 1b ; RPh, 1c ) were prepared. Further reaction of 1a , 1b or 1c with Co 2 (CO) 8 in refluxing toluene gave another three new butterfly compounds [Co 2 Mo 2 (μ 4 -C 2 HPh)(μ-CO) 4 (CO) 4 (η 5 -C 5 H 4 C(O)R) 2 ] (RMe, 2a ; ROEt, 2b ; RPh, 2c ). All of these compounds were characterized fully by elemental analysis, IR and 1 H-NMR. The crystal structures of 1a and 2a were determined by X-ray diffraction techniques. Both 1a and 2a crystallized in monoclinic, with space group P 2 1 (#4), a =7.671(2), b =8.365(2), c =18.308(3) A, β =98.34(1)°, V =1162.3(5) A 3 , Z =2 for 1a and space group P 2 1 / a (#14), a =14.165(5), b =12.498(2), c =16.204(2) A, β =96.50(2)°, V =2850(1) A 3 , Z =4 for 2a.

Synthesis and characterization of novel organometallic compounds containing linked clusters. The molecular structure of (CO)8LCo2M(μ3-C)C(O)OCH2(μ-CCH)Co2(CO)6 [M=Co, W; L=CO, η5-C5H5]

Abstract A novel cluster compound (CO) 9 Co 3 (μ 3 -C)C(O)OCH 2 (μ-CCH)Co 2 (CO) 6 1 and a known cluster compound (CO) 9 Co 3 (μ 3 -C)CH 2 CH 3 2 were obtained by the reaction of Co 2 (CO) 8 with propargyl trichloroacetate. The formation of compound 2 probably involves the cleavage of the two linked clusters in compound 1 . By treating compound 1 with NaW(CO) 3 C 5 H 4 R (R=H, C(O)Me, C(O)C 6 H 4 C(O)OMe) or NaW(CO) 3 C 5 H 4 C(O)C 6 H 4 C(O)C 5 H 4 (CO) 3 WNa in THF at room temperature, five new metal exchange products (CO) 8 (C 5 H 4 R)Co 2 W(μ 3 -C)C(O)OCH 2 (μ-CCH)Co 2 (CO) 6 (R=H, 3a ; R=C(O)Me, 3b ; R=C(O)C 6 H 4 C(O)OMe, 3c ), (CO) 7 (C 5 H 5 ) 2 CoW 2 (μ 3 -C)C(O)OCH 2 (μ-CCH)Co 2 (CO) 6 4 and p -[(CO) 6 Co 2 (μ-CHC)CH 2 OC(O)(μ 3 -C)Co 2 W(CO) 8 C 5 H 4 C(O)] 2 C 6 H 4 5 were obtained. The results indicate that Co(CO) 3 unit in different cluster cores has a different reactivity. All the compounds were characterized by C/H analyses, IR and 1 H-NMR. The molecular structures of 1 and 3a were determined by X-ray structure analyses. Both 1 and 3a are triclinic, space group, P 1 (#2), Z =2, with a =13.191(6) A, b =13.324(4) A, c =7.960(6) A, α =100.86(3)°, β =93.49(2)°, γ =76.46(3)°, V =1335.55 A 3 , final R =0.074, R w =0.104 for 1 and a =8.079(2) A, b =8.154(2) A, c =24.102(4) A, α =82.89(2)°, β =85.20(2)°, γ =69.84(2)°, V =1477.5(6) A 3 , final R =0.053, R w =0.058 for 3a .

Synthesis and characterization of the cluster compounds containing double C2M2 (MCo, Mo) cores. The single-crystal X-ray structures of [O(CH2C2H-μ)2][Co2(CO)6]2 and [O(CH2C2H-μ)2][Mo2(C5H5)2(CO)4]2

Abstract The treatment of dipropargyl ether with Co 2 (CO) 8 in hexane at room temperature gave a new cluster [O(CH 2 C 2 H-μ) 2 ][Co 2 (CO) 6 ] 2 1 , which reacts with the cyclopentadienyl tricarbonyl molybdenum anion [Mo(C 5 H 5 )(CO) 3 ] − to form the hetero-tetranuclear clusters [O(CH 2 C 2 H-μ) 2 ][Co 2 (CO) 6 ][CoMo(C 5 H 5 )(CO) 5 ] 2 and [O(CH 2 C 2 H-μ) 2 ][CoMo(C 5 H 5 )(CO) 5 ] 2 3 , respectively. The reaction of Mo 2 (C 5 H 4 R) 2 (CO) 4 (RH, COOCH 2 CH 3 ) with dipropargyl ether gave the homo-dinuclear clusters [HC 2 CH 2 OCH 2 C 2 H-μ][Mo 2 (C 5 H 4 R) 2 (CO) 4 ] (RH 4 , COOCH 2 CH 3 5 ) and homo-tetranuclear clusters [O(CH 2 C 2 H-μ) 2 ][Mo 2 (C 5 H 4 R) 2 (CO) 4 ] 2 (RH 6 , COOCH 2 CH 3 7 ), respectively. The clusters 4 and 5 reacted with Co 2 (CO) 8 to produce the novel tetranuclear clusters [O(CH 2 C 2 H-μ) 2 ][Co 2 (CO) 6 ][Mo 2 (C 5 H 4 R) 2 (CO) 4 ] (RH 8, COOCH 2 CH 3 9 ). All clusters were characterized by C/H analyses and IR and 1 H-NMR spectroscopy and the crystal structures of 1 and 6 · 1/2CH 2 Cl 2 were determined. Crystals of cluster 1 are monoclinic with space group P 2 1 / c , a =18.149(2), b =7.0111(7), c =20.807(2) A, β =115.318(7)°, V =2403.7(5) A 3 , Z =4 and R =0.030, R w =0.031. Crystals of cluster 6 · 1/2CH 2 Cl 2 are triclinic with space group P 1 , a =7.92(3), b =13.360(3), c =17.208(4) A, α =109.15(1), β =92.07(2), γ =93.34(2)°, V =1714.3(9) A 3 , Z =2 and R =0.040, R w =0.049.

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 ...

SYNTHESIS AND CHARACTERIZATION OF BIS(η5-SUBSTITUTED OR UNSUBSTITUTED CYCLOPENTADIENYL) HEXACARBONYLDIMOLYBDENUM-(TUNGSTEN) COMPLEXES

Abstract Through the reaction of Fe2(SO4)3/HOAc aqueous solution with sodium η5-substituted or un-substituted cyclopentadienyltricarbonylmolybdenate(tungstate) salts Na[M(ηS-C5H4R)(CO)3], eight bis(η5-substituted or unsubstituted cyclopentadienyl) hexacarbonvldimolybdenum (tungsten) complexes [(η5-C5H4R)(CO)3M]2 (M [dbnd] Mo, R [dbnd] H (1), COH (2), COC6H5 (3), COC6H4COOCH3 (4); M [dbnd] W, R [dbnd] H (5), COH (6), COC6H5 (7), COC6H4COOCH3 (8)) were prepared and characterized by analysis, IR and 1H NMR spectra. The molecular structure of complex (3) was determined by single-crystal X-ray methods.

PREPARATION AND CHARACTERIZATION OF CLUSTER COMPLEXES CONTAINING ONE OR TWO C2M2 (M = CO, MO) CORES

Abstract The reaction of dipropargylether with Mo2(C5H4R)2(CO)4 (R = H, COOCH2CH3), prepared by refiuxing a toluene solution of Mo2(C5H4R)2(CO)6 (R = H, COOCH2CH3), gave dinuclear cluster complexes (HC2CH2OCH2C2H-μ)[Mo2(C5H4R)2(CO)4] [(1): R = H, (2): R = COOCH2-CH3] and tetranuclear cluster complexes [Mo2(C5H4R)2(CO)4](μ-HC2CH2OCH2C2H-μ) [Mo2(C5H4R)2(CO)4] [(3): R = H, (4): R = COOCH2CH3], respectively. When (1) or (2) was treated with an equimolar amount of octacarbonyldicobalt, the new novel tetranuclear cluster complexes [Co2CO)6](μ-HC2CH2OCH2C2H-μ)(Mo2(C5H4R)2(CO)4] [(5): R = H, (6): R = COOCH2CH3] were obtained. These complexes were characterized by elemental analysis, IR and 1H NMR spectra. The molecular structure of complex (3 1/2CH2C12) was determined by single-crystal X-ray diffraction methods.

Syntheses and Reactions of Dimolybdenum Propargyl Alcohol Compounds Containing Functionally Substituted Ligands

Abstract Several dimolybdenum propargyl alcohol compounds containing functionally substituted cyclopentadienyl ligands, [Mo2(μ-CHCCH2OH)(CO)4., (η5-C5H4C(O)R)2] [R = OEt, (1); R = Me, (2); R = Ph, (3)J, were synthesized by reactions of propargyl alcohol with [Mo(CO)2(η5-C5H4C(O)R)2] (R = OEt, Me, Ph). The further reactions of these compounds with Co2(CO)8 in refluxing toluene were investigated. From the reaction of compound (1) with Co2(CO)8, a new butterfly compound, [Co2Mo2(μ4-CHCCH2OH)(μ-CO)4(CO)4(η5-C5H4C-(O)OEt)2] (4), was isolated. The structure of compound (2) was determined by a single-crystal X-ray diffraction analysis. The crystal data for compound (2) are: monoclinic, space group P1,21a (#14), a = 10.489(2) Å, b = 11.904(2) Å, c = 16.488(3) Å, β = 91.39(1)°, V = 2058.2(6) Å3, Z = 4, D c = 1.853 g cm−3, R = 0.032 and R w = 0.042.

THE REACTION OF OCTACARBONYLDICOBALT AND PROPARGYL TRICHLOROACETATE

Abstract The reaction of octacarbonyldicobalt and propargyl trichloroacetate gave the expected unknown compound (CO)9Co3(μ3-C)C(O)OCH2(7μ-CCH)Co2(CO)6 (1) and the unexpected known compound (CO)9Co3(μ3-C)CH2CH3 (2). Both (1) and (2) were characterized by elemental analysis and 1H NMR spectra. The molecular structure of (1) was determined by single-crystal X-ray diffraction methods.