68185-45-5

Upstream product

• 33320-28-4 sodium formylcyclopentadienide 
• 13939-06-5 molybdenum hexacarbonyl 
• 201230-82-2 carbon monoxide 

Downstream Products

• 108036-61-9 (μ3-C(C6H5))RuCoMoCp(CO)8H 
• 12078-25-0 dicarbonylcyclopentadienylcobalt 

Relevant academic research and scientific papers

Regiospecific and sequential P-C bond activation/cluster transformations in the reaction of PhCCo2MoCp(CO)8 with the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf)

Thermolysis of the mixed-metal cluster PhCCo2MoCp(CO)8 (1) with the diphosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) in CH2Cl2 leads to the sequential formation of the phosphido-bridged cluster Co2MoCp(CO)5[μ2,η2, η1-C(Ph)C{double bond, long}C(PPh2)C(O)OC(O)](μ-PPh2) (3) and the bis(phosphido)-bridged cluster Co2MoCp(CO)4[η3,η1, η1-C(Ph)C{double bond, long}CC(O)OC(O)](μ-PPh2)2 (4). 3 and 4 have been isolated and characterized in solution by IR and NMR (1H, 13C, and 31P) spectroscopies, and the solid-state structures have been established by X-ray diffraction analyses. Both clusters contain 48e- and exhibit triangular Co2Mo cores. The structure of 3 reveals the presence of a phosphido moiety that bridges the Co-Co vector and a six-electron μ2,η2,η1-C(Ph)C{double bond, long}C(PPh2)C(O)OC(O) ligand that caps one of the Co2Mo faces. The X-ray structure of 4 confirms that the five-electron η3,η1,η1- C(Ph)C{double bond, long}CC(O)OC(O) ligand is σ-bound to the two cobalt centers in an η1 fashion and π-coordinated to the molybdenum center through a traditional η3-allylic interaction. The reaction between PhCCo2MoCp(CO)8 and the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) proceeds similarly, furnishing the phosphido-bridged cluster Co2MoCp(CO)5 [μ2,η2,η1-C(Ph)C{double bond, long}C(PPh2)C(O)OCH(OMe)](μ-PPh2) (6), followed by conversion to Co2MoCp(CO)4[η3,η1, η1-C(Ph)C{double bond, long}CC(O)OCH(OMe)](μ-PPh2)2 (7). The identities of clusters 6 and 7 have been ascertained by solution spectroscopic methods and X-ray crystallography. The overall molecular structure of cluster 6 is similar to that of cluster 3, except that the P-C(furanone ring) bond cleavage occurs with high regioselectivity and high diastereoselectivity. The cleavage of the remaining P-C(furanone ring) bond in cluster 6 gives rise to the bis(phosphido)-bridged cluster 7, whose structure is discussed relative to its bma-derived analogue 4. The diastereoselectivity that accompanies the formation of 6 and 7 is discussed relative to steric effects within the Co2Mo polyhedron. The cyclic voltammetric properties of cluster 3 have been examined, with three well-defined one-electron processes for the 0/+1, 0/-1, -1/-2 redox couples found. The composition of the HOMO and LUMO in 3 was established by extended Hu?ckel MO calculations, with the data discussed relative to the parent tetrahedrane cluster 1.

Study on the reaction of the (μ3-CPh)Co3(CO)9 cluster with NaM(CO)3(η5-RCOCp): Synthesis, characterization and crystal structures of the hetero-nuclear trimetal carbonyl clusters (μ3-CPh)Co2M(CO)8(η5-RCOCp) (M=Mo, W; R=H, CH3, C2H5O)

Six μ3-benzylidyne trimetal carbonyl clusters (μ3-CPh)Co2M(CO)8(η5-RCOCp) (2a: M=Mo, R=H; 3a: M=Mo, R=CH3; 4a: M=Mo, R=C2H5O; 2b: M=W, R=H; 3b: M=W, R=CH3; 4b: M=W, R=C2H5O) were obtained by refluxing a solution of the precursor (μ3-CPh)Co3(CO)9 with the metal exchange reagents NaM(CO)3(η5-RCOCp) in THF. The results show that the electron-withdrawing groups RCO on cyclopentadienyl affected the activity of the metal exchange reagents NaM(CO)3(η5-RCOCp) and the above reactions were accelerated thermally. The results further show that the metal carbonyl unit Co(CO)3 in the precursor PhCCo3(CO)9 could be exchanged by organometallic groups M(CO)2(RCOCp). The clusters were characterized by C/H analysis, IR and 1H NMR, and crystal structure determinations of clusters 3a and 4a. The crystals of 3a are triclinic with space group P1, a=13.631(4), b=14.563(4), c=14.684(6) A, α=116.36(2), β=106.82(2), γ=100.58(2)°, V=2328 A3 and Z=4; final R and Rw=0.052 and 0.061 for 8552 reflections. The crystals of 4a are monoclinic with space group P21/c, a=11.356(2), b=14.030(2), c=16.076(3) A, γ=107.19(1)°, V=2446.8(7) A3 and Z=4; final R and Rw=0.048 and 0.057 for 4751 reflections.

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)

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(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 in THF under reflux followed by acidic treatment with 40percent H3PO4 yielded three new chiral clusters (μ-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 P21/c, a=11.356(2) Angstroem, b=14.030(2) Angstroem, c=16.076(3) Angstroem, β=107.19(1)deg, V=2446.8(7) Angstroem3 and Z=4; final R=0.048 and Rw=0.057 for 4751 reflections.Cluster 7 is monoclinic with space group P21/c, a=12.167(5) Angstroem, b=14.032(7) Angstroem, c=15.159(7) Angstroem, β=105.21(3)deg, V=2497(2) Angstroem3 and Z=4; final R=0.0468 and Rw=0.0410 for 3959 reflections.Keywords: Carbonyl; Chirality; Cluster; Cyclopentadienyl; Transition metal; XRD crystal analysis

Multiple Metal Exchange for μ3-Methylidyne Tricobalt Clusters

The complexes RCCo3(CO)9 (1, R = Me, Ph, CO2Me, C(O)Ph, CO2Ph) were treated with the known metal exchange reagents 2, 2 (M = Mo, W), and Cp(CO)3M-AsMe2 (M = Mo, W) as well as with the new metal exchange reagent NaMCp(CO)3 (M = Mo, W).In stepwise reactions, via the mostly known Co2M clusters (M = Ni, Mo, W), several new clusters of the types RCCoNi2Cp2(CO)3 (5) and RCCoM2Cp2(CO)7 (6, 7, M = Mo, W) could be obtained.In some cases in moderate yields triple metal exchange with formation of the clusters RCNi3Cp3 (12, R = CO2Me) and RCMo3Cp3(CO)6 (13, R = Me, Ph, CO2Me) was achieved.The commonest side reaction was cyclopentadienyl transfer, by which also the new tetranuclear cluster type RCCo3MoCp2(CO)7 (11) was formed which was confirmed by a crystal structure analysis.Structure determinations of one cluster each with Co2Ni, CoNi2, Ni3, and CoMo2 framework completed the structural systematics of these compounds.

Basic Cluster Reactions: Opening and Partial Fragmentation of Tetranuclear Clusters by CO

The influence of CO on 16 mixed tetranuclear clusters of the general type M4(μ3-E)(μ2-AsMe2) with M = Co, Fe, Ru, Mo, W, and E = S, PR, CR is reported.In all cases fragmentation with formation of trinuclear clusters occurs at slightly elevated pressures, during which a Co-As unit is normally eliminated.At normal pressure intermediates are observed in 7 cases, 4 of which can be isolated.Crystal structure analysis of the intermediate FeCo2SAsMe2Cp(CO)10 (8a) has shown that two metal-metal bonds are opened upon addition of CO with formation of the new EM3(μ-AsM) cluster framework.Under vacuum the intermediates are reconverted to the starting clusters with elimination of CO.

Cluster Construction: Synthesis of Tetranuclear Clusters via Aggregation

Trinuclear clusters with EM3 frameworks (1 - 3, EM3 = SFeCo2, SRuCo2, PFeCo2, CCo3) can be connected via CO substitution with AsM'units (M'= Cr, Mo, W).The EM3 - AsM' intermediates 7 - 10 eliminate CO under appropriate conditions to form clusters 13 - 16 with tetrahedral M3M' frameworks which bear μ3-E and μ2-AsMe2 ligands.The combinations M3M'= FeCo2Mo, FeCo2W, RuCo2Mo, RuCo2W, Co3Mo, and Co3W were realized.Starting from trinuclear clusters 4, 5 with the chiral frameworks EM3 = SFeCoMo, SFeCoW, SRuCoMo, and SRuCoW by the same procedure via 11, 12 tetranuclear clusters 17, 18 with the frameworks M3M'= FeCoMo2, FeCoW2, FeCoMoW, RuCoMo2, RuCoW2, and RuCoMoW are obtained.Among these are the first two clusters with four different metal atoms.The crystal structures of FeCo2MoS(AsMe2)Cp(CO)8 (13a), RuCo2MoS(AsMe2)Cp(CO)8 (14a), and FeCoMoWS(AsMe2)Cp2(CO)7 (17b) were determined.The tetranuclear clusters show ligand fluxionality as shown by dynamic 1H NMR spectroscopy.

Mixed Metal Clusters: Metal Exchange via Organometal Dimethylarsenides

Reactions of the methylidyne-tricobalt clusters YCCo3(CO)9 (1, Y = H, Me, Ph, p-Tol, F) with the organometal dimethylarsenides Cp(CO)3M - AsMe2 (2 - 4, M = Cr, Mo, W) initially yield the addition products 5 - 7 through CO replacement.From these by heating a Co - As fragment is eliminated, whereby the new mixed metal clusters YCCo2MCp(CO)8 (9 - 11) are formed.Of the MeCCo2Mo compound 10c the molecular structure was determined.The mixed metal clusters allow for CO substitution by which also their prochirality can be proved.Attempts to perform corresponding metal exchange reactions with other tetrahedral cobalt clusters (PhPCo3(CO)9, Co4(CO)12, HFeCo3(CO)12, CpNiCo3(CO)9) or with other organometal dimethylarsenides M - AsMe2 (M = Cp(CO)2Fe, (CO)5Mn, Me3P(CO)4Mn) were only partially successful.