The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster wit...The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster with ferracyclopentadiene ring（μ_2, η~4-C_4Ph_4）Fe_2（CO）_6（1） and one tetraphenyl substituted cyclopentadienone（Ph_4C_4CO）（2） were simultaneously obtained by the reaction of Fe_3（CO）_（12） with alkyne（Ph-C≡C-Ph）. Only one ferrole cluster（μ_2, η~4-C_4Fc_2H_2）Fe_2（CO）_6（3） was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex（η~4-C_4Fc_4CO）Fe（CO）_3（4） and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3（CO）_2]（5） were obtained by using Fc-C≡C-Fc as alkyne. A new complex（η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one）-tricarbonyl iron（η~4-C_4Ph_2Fc_2CO）Fe（CO）_3（6） was synthesized by the reaction of Fe_3（CO）_（12） with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.展开更多
The cluster complex (μ4-η2-C2Ph2) Co4 (CO)8 (μ-CO)2 was synthesized by 'one pot' method starting from Co2(CO)8 and PhCCPh in toluene and characterized by single-crystal structure analysis. It crystallizes i...The cluster complex (μ4-η2-C2Ph2) Co4 (CO)8 (μ-CO)2 was synthesized by 'one pot' method starting from Co2(CO)8 and PhCCPh in toluene and characterized by single-crystal structure analysis. It crystallizes in the monoclinic space group P21/c with a=9. 149(3). b=11. 732(2), c=23.551 (6) A, β=92. 62(2)°, V=2525 (1), Z=4, Dc= 1. 83 g/cm3,Mr = 694. 07.μ=26.33cm-1,F(000)=1368. The final R= 0. 039, Rω= 0. 047 for 2812 observed independent reflections(I≥3σ(I)). In the molecule, four cobalt atoms form a butterflyshaped metal skeleton and the ligand C2Ph2 is coordinated to cobalt atoms through two σ bonds and a delocalized four- center π-bonding system.展开更多
The reaction of octacarbonyldicobalt and dipropargyl malonate afforded the two expected compounds [CH 2(CO 2CH 2C 2H\|μ) 2][Co 2(CO) 6] 2 1 and [HC 2CH 2O(O)C^CH 2CO 2CH 2C 2H\|μ][Co 2(CO) 6)] 2. Bot...The reaction of octacarbonyldicobalt and dipropargyl malonate afforded the two expected compounds [CH 2(CO 2CH 2C 2H\|μ) 2][Co 2(CO) 6] 2 1 and [HC 2CH 2O(O)C^CH 2CO 2CH 2C 2H\|μ][Co 2(CO) 6)] 2. Both 1 and 2 were characterized by elemental analysis, IR and NMR. The molecular structure of 1 was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with the following crystallographic parameters~: a=7.7492(15), b=12.925(3), c=14.366(3) , α=81.92(3), β=77.94(3), γ=89.48(3)°, V=1392.9(5) 3, Z= 2, M r=751.99, D c=1.793 g/cm 3, F(000)=740, μ(Mo-Kα)=24.13 cm -1 and final R=0.0880 for 5421 observations with I>2σ(I).展开更多
Oxidative-decarbonylation of Co2(CO) 6(μ-PhC≡CH) with Me3NO in the presence of an electron deficient ligand, Ph2PC5F6PPh2 (F6FOS), produces Co2 (CO) 4 (μ-PhC≡CH)(F6FOS), (1). The metrical values of 1 have been com...Oxidative-decarbonylation of Co2(CO) 6(μ-PhC≡CH) with Me3NO in the presence of an electron deficient ligand, Ph2PC5F6PPh2 (F6FOS), produces Co2 (CO) 4 (μ-PhC≡CH)(F6FOS), (1). The metrical values of 1 have been compared to those of the closely related cobalt carbonyl alkyne compound A containing (Z)-Ph2PCH=CHPPh2 (Z-dppe) ligand. Strikingly anomalous is an alkyne C≡C bond (1.34(1) ? in 1, which is somewhat elongated compared to A (1.31(1) ?). When taking a strong electron-withdrawing power of fluoride atom into account, F6FOS ligand appeared to reduce the π-back-donation ability of cobalt atom, making this bond shortened in comparison to the same bond in A. Bond lengthening in the alkyne C≡C bond in 1 is attributed to the enhanced electron donor ability of F6FOS compared to Z-dppe and can be understood by examining resonance structures of F6FOS ligand.展开更多
The reaction of dipropargyl phthalate C6H41,2(CO2CH2C2H)2 1 with octacarbonyldicobalt 2 resulted in the formation of red complex C6H41,2(CO2CH2C2H)2Co2(CO)62 3, in which each Co2(CO)6 group coordinates to one of t...The reaction of dipropargyl phthalate C6H41,2(CO2CH2C2H)2 1 with octacarbonyldicobalt 2 resulted in the formation of red complex C6H41,2(CO2CH2C2H)2Co2(CO)62 3, in which each Co2(CO)6 group coordinates to one of the two CC bonds of 1. Molecular structure of complex 3 was determined by single crystal Xray analyses. The crystal belongs to the monoclinic system, space group P21/a with the following crystallographic parameters: a=8.521(2), b=29.143(6), c=12.918(7) , = 100.12(3),V=3158(2) 3, Z=4, Mr=814.09, Dc=1712 g.cm-3, F(000)=1608, (MoK)=21.37 cm-1 and final R=0.044 for 3151 observations.展开更多
The substituted reactions of (μ-FcC≡CH)Co2(CO)6 with PPh3, AsPh3 and dppm have been studied and three new substituted derivatives have been obtained. The compounds were characterized by elemental analysis, IR, 1H NM...The substituted reactions of (μ-FcC≡CH)Co2(CO)6 with PPh3, AsPh3 and dppm have been studied and three new substituted derivatives have been obtained. The compounds were characterized by elemental analysis, IR, 1H NMR, MS and X-ray crystallography. They have the following formula: (μ-FcC≡CH)Co2(CO)6-nL[n=1, L=PPh3(2), AsPh3 (3); n=2, L=dppm (4)]. The cluster 2 crystallizes in monoclinic, space group P21/n, with a=1.342 4(8) nm, b=1.305 4(8) nm, c=1.875 0(9) nm, β=103.084(9)°, V=3.201(3) nm3, Z=4, F(000)=1 480, Dc=1.515 g·cm-3, μ=15.62 cm-1; final R indices [I > 2σ(I)]: R1=0.040 9, ωR2=0.076 9; S=1.007, Δρmax=463 e·nm-3, Δρmin=-395 e·nm-3. The cluster 3 crystallizes in monoclinic, space group P21/n, with a=1.341 0(4) nm, b=1.307 9(4) nm, c=1.912 0(5) nm, β=103.043(5)°, V=3.267(15) nm3, Z=4, F(000)=1 552, Dc=1.574 g·cm-3, μ=24.87 cm-1; final R indices[I > 2σ(I)]:R1=0.043 7, ωR2=0.078 2; S=0.995, Δρmax=530 e·nm-3, Δρmin=-444 e·nm-3. CCDC: 221860, 2; 221863, 3.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21266019,21062011 and 21462029)Inner Mongolia Autonomous Region Higher Scientific Research Project(NJZY14060)
文摘The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster with ferracyclopentadiene ring（μ_2, η~4-C_4Ph_4）Fe_2（CO）_6（1） and one tetraphenyl substituted cyclopentadienone（Ph_4C_4CO）（2） were simultaneously obtained by the reaction of Fe_3（CO）_（12） with alkyne（Ph-C≡C-Ph）. Only one ferrole cluster（μ_2, η~4-C_4Fc_2H_2）Fe_2（CO）_6（3） was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex（η~4-C_4Fc_4CO）Fe（CO）_3（4） and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3（CO）_2]（5） were obtained by using Fc-C≡C-Fc as alkyne. A new complex（η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one）-tricarbonyl iron（η~4-C_4Ph_2Fc_2CO）Fe（CO）_3（6） was synthesized by the reaction of Fe_3（CO）_（12） with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.
文摘The cluster complex (μ4-η2-C2Ph2) Co4 (CO)8 (μ-CO)2 was synthesized by 'one pot' method starting from Co2(CO)8 and PhCCPh in toluene and characterized by single-crystal structure analysis. It crystallizes in the monoclinic space group P21/c with a=9. 149(3). b=11. 732(2), c=23.551 (6) A, β=92. 62(2)°, V=2525 (1), Z=4, Dc= 1. 83 g/cm3,Mr = 694. 07.μ=26.33cm-1,F(000)=1368. The final R= 0. 039, Rω= 0. 047 for 2812 observed independent reflections(I≥3σ(I)). In the molecule, four cobalt atoms form a butterflyshaped metal skeleton and the ligand C2Ph2 is coordinated to cobalt atoms through two σ bonds and a delocalized four- center π-bonding system.
文摘The reaction of octacarbonyldicobalt and dipropargyl malonate afforded the two expected compounds [CH 2(CO 2CH 2C 2H\|μ) 2][Co 2(CO) 6] 2 1 and [HC 2CH 2O(O)C^CH 2CO 2CH 2C 2H\|μ][Co 2(CO) 6)] 2. Both 1 and 2 were characterized by elemental analysis, IR and NMR. The molecular structure of 1 was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with the following crystallographic parameters~: a=7.7492(15), b=12.925(3), c=14.366(3) , α=81.92(3), β=77.94(3), γ=89.48(3)°, V=1392.9(5) 3, Z= 2, M r=751.99, D c=1.793 g/cm 3, F(000)=740, μ(Mo-Kα)=24.13 cm -1 and final R=0.0880 for 5421 observations with I>2σ(I).
文摘Oxidative-decarbonylation of Co2(CO) 6(μ-PhC≡CH) with Me3NO in the presence of an electron deficient ligand, Ph2PC5F6PPh2 (F6FOS), produces Co2 (CO) 4 (μ-PhC≡CH)(F6FOS), (1). The metrical values of 1 have been compared to those of the closely related cobalt carbonyl alkyne compound A containing (Z)-Ph2PCH=CHPPh2 (Z-dppe) ligand. Strikingly anomalous is an alkyne C≡C bond (1.34(1) ? in 1, which is somewhat elongated compared to A (1.31(1) ?). When taking a strong electron-withdrawing power of fluoride atom into account, F6FOS ligand appeared to reduce the π-back-donation ability of cobalt atom, making this bond shortened in comparison to the same bond in A. Bond lengthening in the alkyne C≡C bond in 1 is attributed to the enhanced electron donor ability of F6FOS compared to Z-dppe and can be understood by examining resonance structures of F6FOS ligand.
文摘The reaction of dipropargyl phthalate C6H41,2(CO2CH2C2H)2 1 with octacarbonyldicobalt 2 resulted in the formation of red complex C6H41,2(CO2CH2C2H)2Co2(CO)62 3, in which each Co2(CO)6 group coordinates to one of the two CC bonds of 1. Molecular structure of complex 3 was determined by single crystal Xray analyses. The crystal belongs to the monoclinic system, space group P21/a with the following crystallographic parameters: a=8.521(2), b=29.143(6), c=12.918(7) , = 100.12(3),V=3158(2) 3, Z=4, Mr=814.09, Dc=1712 g.cm-3, F(000)=1608, (MoK)=21.37 cm-1 and final R=0.044 for 3151 observations.
文摘The substituted reactions of (μ-FcC≡CH)Co2(CO)6 with PPh3, AsPh3 and dppm have been studied and three new substituted derivatives have been obtained. The compounds were characterized by elemental analysis, IR, 1H NMR, MS and X-ray crystallography. They have the following formula: (μ-FcC≡CH)Co2(CO)6-nL[n=1, L=PPh3(2), AsPh3 (3); n=2, L=dppm (4)]. The cluster 2 crystallizes in monoclinic, space group P21/n, with a=1.342 4(8) nm, b=1.305 4(8) nm, c=1.875 0(9) nm, β=103.084(9)°, V=3.201(3) nm3, Z=4, F(000)=1 480, Dc=1.515 g·cm-3, μ=15.62 cm-1; final R indices [I > 2σ(I)]: R1=0.040 9, ωR2=0.076 9; S=1.007, Δρmax=463 e·nm-3, Δρmin=-395 e·nm-3. The cluster 3 crystallizes in monoclinic, space group P21/n, with a=1.341 0(4) nm, b=1.307 9(4) nm, c=1.912 0(5) nm, β=103.043(5)°, V=3.267(15) nm3, Z=4, F(000)=1 552, Dc=1.574 g·cm-3, μ=24.87 cm-1; final R indices[I > 2σ(I)]:R1=0.043 7, ωR2=0.078 2; S=0.995, Δρmax=530 e·nm-3, Δρmin=-444 e·nm-3. CCDC: 221860, 2; 221863, 3.
