Wei-Qiang 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.

Synthesis, reaction and enantiomeric resolution of chiral clusters containing SRuNiM (M = Mo, W) core

Abstract The treatment of [(η5-C5H4R)CoRuM(CO)8(μ3-S)] with NiCp2 in THF at refluxing temperature gives six novel clusters containing functionally substituted cyclopentadienyl ligand [(η5-C5H5)(η5-C5H4COR)NiRuM(CO)5(μ3-S)] (1, M=Mo, R=CH3; 2, M=W, R=CH3; 3, M=Mo, R=OC2H5; 4, M=W, R=OC2H5; 5, M=Mo, R=COC6H4COOCH3; 6 M=W, R=COC6H4COOCH3). The reactions of clusters (1–6) with 2,4-dinitrophenylhydrazine were investigated. The ester group was difficult to hydrolyze (clusters 3–6). Hydrazide can easily condense with the ketonic carbonyl (cluster 1 and 2) on the cyclopentadienyl ring to form complexes [(η5-C5H5)(η5-C5H4C(NR)CH3)NiRuM(CO)5(μ3-S)] (7, M=Mo, R=NH-C6H3-2,4-(NO2)2; 8, M=W, R=NHC6H3-2,4-(NO2)2). The structures of 1, 2 and 7 have been established by the single crystal X-ray diffraction method and the enantiomers of chiral complexes 1, 3 and 5 were successfully separated by liquid chromatography.

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 resolution of a tetrahedral cluster containing the SeRuCoMo core

A new cluster derivative (μ3-Se)RuCoMo(CO)8CpCOOCH3 3 was obtained by the reaction of SeRuCo2(CO)9 1 with the functionally-substituted sodium cyclopendiene [Mo(CO)8CpCOOCH3]Na 2 in THF at 60°C and its structure has been determined by single-crystal X-ray diffraction.

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.

The synthesis of tetrahedral clusters SOsCo2(CO)9, relevant to chiral tetrahedral clusters containing the SOsCoW core

A simple route to synthesise clusters [SOsCo2(CO)9] in excellent yield and mild reaction conditions is described. Several new chiral tetrahedral clusters containing the Os element were synthesised by the thermal reaction of the precursor [(μ3-S)OsCo2(CO)9] with the functionally-substituted metal exchange reagents. The structure of cluster [(μ3-S)OsCoW(CO)8C5H4C(O)CH3] was established by X-ray single crystal diffraction.

Reactions of trans-Carbonyl(Chloro)-[Bis(Triphenylphosphine)]Rhodium(I) with Substituted Cyclopentadienyl Tricarbonyl Molybdenum Anions

Reactions of trans-carbonyl(chloro)[bis(triphenylphosphine)]rhodium(I): trans-ClRh(CO)(PPh3)2 with substituted cyclopentadienyl tricarbonyl molybdenum anions, [Mo(CO)3(η 5 -C5H4R)]− (R=H; COCH3) in tetrahydrofuran (THF) at 55°C for 24 h yielded two monometallic complexes as by-products: [Rh(CO)(PPh3)(η5-C5H4R)] (R = H (1a); COCH3 (2a)) and two main heterobimetallic compounds: [RhMo(CO)4(PPh3)2(η5-C5H4R)] (R = H (1b); COCH3 (2b)). These compounds were characterized by elemental analysis, IR and 1H NMR spectra. The molecular structure of (2a) was determined by X-ray diffraction.

Synthesis and crystal structure of a new butterfly cluster [Rh2Co2 (CO)6(μ-CO)4(μ4,η2-HC≡CFeCp2)]

The new butterfly cluster [Rh2Co2(CO)6(μ-CO)4(μ4, η2-HC≡CFeCp2)] 3 was obtained by the reaction of [Rh2Co2(CO)12] 1 with the 1-alkyne ligand HC≡CFeCp2 2, and the structure of cluster 3 has been established by single-crystal X-ray diffraction methods.

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.