Through the reaction of Co 2(CO) 8 with four ligands containing P ?S? N atoms, cobalt carbonyl sulfur clusters Co 3(CO) 7( μ 3-S)〔 μ,η 2 -CNC(CH 3) 2P(S)(Cl)N(Ph)](Ⅰ)and Co 3 (CO) 7( μ 3-S)〔 μ,η 2 -SC(NH2)N-N...Through the reaction of Co 2(CO) 8 with four ligands containing P ?S? N atoms, cobalt carbonyl sulfur clusters Co 3(CO) 7( μ 3-S)〔 μ,η 2 -CNC(CH 3) 2P(S)(Cl)N(Ph)](Ⅰ)and Co 3 (CO) 7( μ 3-S)〔 μ,η 2 -SC(NH2)N-N=CH-C 6H 5〕 (Ⅱ),two tetranu-clear cobalt carbonyl clusters Co 4(CO) 10( μ 4 -S)( μ 4 -PC 6H 4OCH 3)(Ⅲ) and Co 4(CO) 10( μ 4-S)( μ 4-PC 6H 4OC 2H 5)(Ⅳ) ,were prepared and characterized by elementary analysis?IR? 1HNMR and MS spectroscopy.It was shown that bothⅠand Ⅱ have a tetrahedral framework Co 3S , both Ⅲ and Ⅳ have a octahedral framework Co 4SP. (Ⅰ)and Co 3 (CO) 7( μ 3-S)〔 μ,η 2 -SC(NH2)N-N=CH-C 6H 5〕 (Ⅱ),two tetranu-clear cobalt carbonyl clusters Co 4(CO) 10( μ 4 -S)( μ 4 -PC 6H 4OCH 3)(Ⅲ) and Co 4(CO) 10( μ 4-S)( μ 4-PC 6H 4OC 2H 5)(Ⅳ) ,were prepared and characterized by elementary analysis?IR? 1HNMR and MS spectroscopy.It was shown that bothⅠand Ⅱ have a tetrahedral framework Co 3S , both Ⅲ and Ⅳ have a octahedral framework Co 4SP.展开更多
The reaction of Co 2(CO) 8 with organic hetrocyclic dithiophosphinate,SP(Fc)(S)N(C 6H 5)NC(Me),gave three cobalt carbonyl cluster derivatives,Co 4(CO) 8(μ CO) 2(μ 4 S)[μ 4 P(Fc)]f,Co 4(CO) 10 (μ 3 S)[μ η 2 P(Fc)...The reaction of Co 2(CO) 8 with organic hetrocyclic dithiophosphinate,SP(Fc)(S)N(C 6H 5)NC(Me),gave three cobalt carbonyl cluster derivatives,Co 4(CO) 8(μ CO) 2(μ 4 S)[μ 4 P(Fc)]f,Co 4(CO) 10 (μ 3 S)[μ η 2 P(Fc)N(C 6H 5)NC(Me)] and Co 2(CO) 5[μ η 2 P(Fc)N(C 6H 5)NC(Me)].These clusters were characterized by elementary analysis,IR, 1HNMR and MS spectroscopy.During the reaction,the precursor was cleaved in its P=S,P S,P N and C S bonds,respectively,to give the fragments as ligands as listed above that coordinated to Co atoms to form the new cluster molecules.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
文摘Through the reaction of Co 2(CO) 8 with four ligands containing P ?S? N atoms, cobalt carbonyl sulfur clusters Co 3(CO) 7( μ 3-S)〔 μ,η 2 -CNC(CH 3) 2P(S)(Cl)N(Ph)](Ⅰ)and Co 3 (CO) 7( μ 3-S)〔 μ,η 2 -SC(NH2)N-N=CH-C 6H 5〕 (Ⅱ),two tetranu-clear cobalt carbonyl clusters Co 4(CO) 10( μ 4 -S)( μ 4 -PC 6H 4OCH 3)(Ⅲ) and Co 4(CO) 10( μ 4-S)( μ 4-PC 6H 4OC 2H 5)(Ⅳ) ,were prepared and characterized by elementary analysis?IR? 1HNMR and MS spectroscopy.It was shown that bothⅠand Ⅱ have a tetrahedral framework Co 3S , both Ⅲ and Ⅳ have a octahedral framework Co 4SP. (Ⅰ)and Co 3 (CO) 7( μ 3-S)〔 μ,η 2 -SC(NH2)N-N=CH-C 6H 5〕 (Ⅱ),two tetranu-clear cobalt carbonyl clusters Co 4(CO) 10( μ 4 -S)( μ 4 -PC 6H 4OCH 3)(Ⅲ) and Co 4(CO) 10( μ 4-S)( μ 4-PC 6H 4OC 2H 5)(Ⅳ) ,were prepared and characterized by elementary analysis?IR? 1HNMR and MS spectroscopy.It was shown that bothⅠand Ⅱ have a tetrahedral framework Co 3S , both Ⅲ and Ⅳ have a octahedral framework Co 4SP.
文摘The reaction of Co 2(CO) 8 with organic hetrocyclic dithiophosphinate,SP(Fc)(S)N(C 6H 5)NC(Me),gave three cobalt carbonyl cluster derivatives,Co 4(CO) 8(μ CO) 2(μ 4 S)[μ 4 P(Fc)]f,Co 4(CO) 10 (μ 3 S)[μ η 2 P(Fc)N(C 6H 5)NC(Me)] and Co 2(CO) 5[μ η 2 P(Fc)N(C 6H 5)NC(Me)].These clusters were characterized by elementary analysis,IR, 1HNMR and MS spectroscopy.During the reaction,the precursor was cleaved in its P=S,P S,P N and C S bonds,respectively,to give the fragments as ligands as listed above that coordinated to Co atoms to form the new cluster molecules.
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.
