Yu-Hua Zhang

Synthesis and characterization of new rhodium–cobalt mixed-metal octahedral linked clusters containing η2-diyne ligands

Six new RhCo mixed-metal linked cluster complexes [Rh 2 Co 2 (CO) 8 (μ-CO) 2 (μ 4 ,η 2 -HCCCH 2 O)] 2 R (R=C 6 H 4 -1,4 ( 1 ); C 6 H 4 -1,4(C(O)) 2 ( 2 ); (C(O)CH 2 ) 2 ( 3 ); (C(O)CH) 2 ( 4 ); (C(O)) 2 CH 2 ( 5 ); (C(O)) 2 ( 6 )) have been synthesized from reactions of [Rh 2 Co 2 (CO) 12 ] ( 7 ) with the appropriate diyne compounds [(HCCCH 2 CO)] 2 R (R=C 6 H 4 -1,4 ( 8 ); C 6 H 4 -1,4(C(O)) 2 ( 9 ); (C(O)CH 2 ) 2 ( 10 ); (C(O)CH) 2 ( 11 ); (C(O)) 2 CH 2 ( 12 ); (C(O)) 2 ( 13 )) in n -hexane at room temperature, respectively. The acetylene moieties of diyne ligands insert into the CoCo bonds of two tetranuclear clusters to give linked octahedral clusters containing two [Rh 2 Co 2 C 2 ] units. The structure of cluster 1 was determined by single-crystal X-ray diffraction analysis and all clusters were characterized by elemental analysis (C/H), IR and 1 H-NMR spectroscopy.

Study of metal exchange reactions in cobalt containing clusters

Abstract Treatment of the linked cluster {[(μ3-C)R]Co2Mo(CO)8[η5-C5H4C(O)]}2C6H4-p (1a, R=CO2Et; 1b, R=C6H5) with the substituted cyclopentadienyl tricarbonyl molybdenum anion [Mo(CO)3(η5-C5H4R′)]− in THF gave rise to the formation of the single cluster complex [(μ3-C)R]Co2Mo(CO)8(η5-C5H4R′) (2a, R=CO2Et, R′=H; 2b, R=CO2Et, R′=C(O)Me; 2c, R=R′=CO2Et; 2d, R=C6H5, R′=CO2Et) as the only product. However, reaction of cluster {(μ3-Se)RuCoMo(CO)8[η5-C5H4C(O)]}2C6H4-p (1c) with NaMo(CO)3[η5-C5H4C(O)Me] yielded the linked cluster compound (μ3-Se)RuCoMo(CO)8[η5-C5H4C(O)-p-C6H4-C(O)C5H4-η5](CO)7RuMo2(μ3-Se)[η5-C5H4C(O)Me] (3). Further reactions of 2b and cluster [(μ3-C)CO2Et]Co2Mo(CO)8[η5-C5H4C(O)-p-C6H4CO2Me] (2e), respectively, with the monoanion [Mo(CO)3(η5-C5H5)]− gave four products 2a, [(μ3-C)CO2Et]CoMo2(CO)7(η5-C5H5)2 (4), [(μ3-C)CO2Et]CoMo2(CO)8(η5-C5H4R)(η5-C5H5) (5a, R=C(O)Me; 5b, R=C(O)-p-C6H4CO2Me) and [(μ3-C)CO2Et]CoMo2(CO)8(η5-C5H4R)2 (6a, R=C(O)Me). By contrast, treatment of cluster 2a with the monoanion [Mo(CO)3(η5-C5H4R)]− afforded three cluster products 4, 2 (2b, R=C(O)Me; 2e, R=C(O)-p-C6H4CO2Me) and 5 (5a, R=C(O)Me; 5b, R=C(O)-p-C6H4CO2Me). All the compounds were fully characterized by elemental and spectroscopic analyses. The molecular structures of clusters 2a and 4 have been determined by single-crystal X-ray diffraction.

Synthesis of cluster derivatives containing the NiRuMoS core

The new clusters [NiRuMo(CO)5(μ3-S)(η5 –C5H5)(η5 –C5H4R)](R = H 3 or COCH3 4) were isolated from the reaction of [CoRuMo(CO)8(μ3-S) (η5 –C5H4R)](R = H 1 or COCH3 2) with NiCp2, and the structure of cluster 4 has been established by single crystal X-ray diffraction method.

Synthesis of the chiral indenyl tetrahedral clusters [(μ3-S)FeCoM(η5-Ind)(CO)8] (M=Mo,W) and the crystal structure of [(μ3-S)FeCoW(η5-Ind)(CO)8]

The new indenyl tetrahedral cluster [(μ3-S)FeCoM (η5-Ind)(CO)8] (M=Mo 2, W 3) have been isolated from the reaction of [(μ3-S)FeCo2(CO)9] 1 and K+[(η5-Ind)M(CO)3]- (M=Mo,W) under mild conditions and the crystal structure of [(μ3-S)FeCoW(η5-Ind)(CO)8] 3 has been established, affording structural evidence for the ring slippage of the indenyl ligand.

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 reactions of chiral tetrahedral clusters containing an COOCH3 functional group

The new cluster [CoRuW(CO)8(μ3-S)(η5–C5H4COOCH3)] 2 was isolated from the reaction of [Co2Ru(CO)9(μ3-S) 1 with Na[W(CO)3(η5–C5H4COOCH3)]. Through the further reaction of cluster 2 with n-propylamine, a new cluster [CoRuW(CO)8(μ3-S) (η5–C5H4CONH-C3H7)] 3 was obtained and the structure of cluster 2 has been established by single crystal X-ray diffraction.

PREPARATION AND CHARACTERIZATION OF SOME DIMERIC η2-DIYNE COMPLEXES OF COBALT

ABSTRACT The organometallic dimers, [{R(CO2CH2C2H-µ)2}-{Co2(CO)6}2] [R=C6H4−1,4 (1), (CH)2 (2), (CH2)2 (3)], have been prepared from reactions between Co2(CO)8 and appropriate diyne ligands in tetrahydrofuran at room temperature. These complexes have been characterized by IR spectra, 1H NMR spectra and elemental analyses. The structure of (1) was determined by single crystal X-ray diffraction. The compound (1), C26H10O16Co4, Mr=814.06, is triclinic, space group P1¯, with unit cell dimensions a=8.139(2), b=8.803(3), c=11.343(3) Å, α=99.421(6), β=96.260(6), γ=102.772(6)°. The cobalt atom is coordinated by three terminal carbonyls and an alkynyl group. The Co-Co bond length is 2.4834(7) Å.

Syntheses and characterisation of new Rh-Co mixed-metal octahedral linked clusters

The new Rh-Co mixed-metal dimer [Rh2Co2(CO)8(μ-CO)2(μ4,η2-HC≡CCH2O-)]2C6H4 4 and trimer [Rh2Co2(CO)8 (μ-CO)2(μ4,η2-HC≡CCH2O-)]3B 5 have been synthesised from reactions between Rh2Co2(CO)12 1 and the appropriate diyne and triyne ligands. The crystal structure of cluster 4 has been determined.