The reaction of Ru3(CO)12 with P(NEt2)2Cl, yields two trinuclear ruthenium carbonyl clusters: HRu3(CO)9[ μ3-η2-P(NEt2)2]2 Ⅰ (known) and a novel Ru3(CO)7( μ-Cl)2[ μ-P(NEt2)2]2 Ⅱ. During the reaction, the ligand p...The reaction of Ru3(CO)12 with P(NEt2)2Cl, yields two trinuclear ruthenium carbonyl clusters: HRu3(CO)9[ μ3-η2-P(NEt2)2]2 Ⅰ (known) and a novel Ru3(CO)7( μ-Cl)2[ μ-P(NEt2)2]2 Ⅱ. During the reaction, the ligand precursor was cleaved in its P-Cl bond to give the fragments Cl and P(NEt2)2, and then coordinated to the ruthenium atoms to form the clusters as listed above. The crystal structure of cluster Ⅱ has been determined by X-ray diffraction technique. The crystal belongs to monoclinic with space group P21 / c. The unit cell parameters are as follows: a=1.287 9(6) nm, b=1.653 9(8) nm, c=1.643 6(8) nm, β=95.786(7)°, V=3.483(3) nm3, Dc=1.756 g·cm-3, Z=4. The cluster has a closed triangle Ru3 framework. Two Ru-Ru bonds are supported by μ-P(NEt2)2, the other one is connected by double Cl bridging. The valence electrons of the cluster are 50e. CCDC: 231979.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 mono and di substituted derivatives of the parent cluster {μ3 H(Ph)C=C}FeCo2(CO)9 (1) have been synthesized by facile substitution reactions. The compound {μ3 H(Ph)C=C}FeCo2(CO)7(dppe) (2), {μ3 H(Ph)C=C}FeCo2(C...The mono and di substituted derivatives of the parent cluster {μ3 H(Ph)C=C}FeCo2(CO)9 (1) have been synthesized by facile substitution reactions. The compound {μ3 H(Ph)C=C}FeCo2(CO)7(dppe) (2), {μ3 H(Ph)C=C}FeCo2(CO)8(PPh3) (3) and {μ3 H(Ph)C=C}FeCo2(CO)8(AsPh3) (4) were characterized by elemental analysis, IR, 1H ,31P NMR, MS and X ray crystallography. The new cluster 2 crystallizes in monoclinic space group P21/n, with a=0. 8614(5)nm, b=1.6404(8)nm, c=2.6574(14)nm, β=96.3222(12)°, V=3.732(3)nm3, Z=4, S=0.886, Δρmax=0.335e·nm-3, Δρmin=-0.379e·nm-3. Final R indices : R1=0.0432, wR2=0.0695. CCDC: 164600.展开更多
通过配体取代将四核羰基簇FeCo_3(CO)_(12)^-锚联在膦化的聚苯乙烯表面,获得担载簇FeCo(?)(CO)_(11)PPh_3^-/poly,目的在于使簇骼结构偏离较高对称性.以考察锚联过程对簇结构的影响.本文以EXAFS(Extended X-ray Absorption Fine Structu...通过配体取代将四核羰基簇FeCo_3(CO)_(12)^-锚联在膦化的聚苯乙烯表面,获得担载簇FeCo(?)(CO)_(11)PPh_3^-/poly,目的在于使簇骼结构偏离较高对称性.以考察锚联过程对簇结构的影响.本文以EXAFS(Extended X-ray Absorption Fine Structure)方法研究了担载样品的结构.结果显示担载簇与FeCo_3(CO)_(11)PPh_3^-晶体具有相同的结构模式,尤其是膦配体确实与一Co原子相连接.EXAFS结果表明:(1)与FoCo_3(CO)_(12)^-(其簇骼具有三重对称性结构)比较,锚联使Co—Fe键增长0.005nm;金属-金属及金属-桥联碳壳层的Debye-Waller因子均增大约一倍而金属-端联碳壳层的值变化很小.说明金属-金属间实际键长值具有一较宽分布,因而其簇骼已偏离了三重对称结构;(2)与FeCo_3(CO)_(11)PPh_3^-晶体的结构比较.Co—Fe键长长0.003nm.而Co—Co键长则短约0.002nm.考虑到EXAFS分析只能给出平均键长值,因此认为,存在于FeCo_3(CO)_(11)PPh_3^-晶体中的由于一个羰基被膦配体取代而引起的簇骼畸变,在锚联后被加剧.展开更多
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
文摘The reaction of Ru3(CO)12 with P(NEt2)2Cl, yields two trinuclear ruthenium carbonyl clusters: HRu3(CO)9[ μ3-η2-P(NEt2)2]2 Ⅰ (known) and a novel Ru3(CO)7( μ-Cl)2[ μ-P(NEt2)2]2 Ⅱ. During the reaction, the ligand precursor was cleaved in its P-Cl bond to give the fragments Cl and P(NEt2)2, and then coordinated to the ruthenium atoms to form the clusters as listed above. The crystal structure of cluster Ⅱ has been determined by X-ray diffraction technique. The crystal belongs to monoclinic with space group P21 / c. The unit cell parameters are as follows: a=1.287 9(6) nm, b=1.653 9(8) nm, c=1.643 6(8) nm, β=95.786(7)°, V=3.483(3) nm3, Dc=1.756 g·cm-3, Z=4. The cluster has a closed triangle Ru3 framework. Two Ru-Ru bonds are supported by μ-P(NEt2)2, the other one is connected by double Cl bridging. The valence electrons of the cluster are 50e. CCDC: 231979.
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 mono and di substituted derivatives of the parent cluster {μ3 H(Ph)C=C}FeCo2(CO)9 (1) have been synthesized by facile substitution reactions. The compound {μ3 H(Ph)C=C}FeCo2(CO)7(dppe) (2), {μ3 H(Ph)C=C}FeCo2(CO)8(PPh3) (3) and {μ3 H(Ph)C=C}FeCo2(CO)8(AsPh3) (4) were characterized by elemental analysis, IR, 1H ,31P NMR, MS and X ray crystallography. The new cluster 2 crystallizes in monoclinic space group P21/n, with a=0. 8614(5)nm, b=1.6404(8)nm, c=2.6574(14)nm, β=96.3222(12)°, V=3.732(3)nm3, Z=4, S=0.886, Δρmax=0.335e·nm-3, Δρmin=-0.379e·nm-3. Final R indices : R1=0.0432, wR2=0.0695. CCDC: 164600.
文摘通过配体取代将四核羰基簇FeCo_3(CO)_(12)^-锚联在膦化的聚苯乙烯表面,获得担载簇FeCo(?)(CO)_(11)PPh_3^-/poly,目的在于使簇骼结构偏离较高对称性.以考察锚联过程对簇结构的影响.本文以EXAFS(Extended X-ray Absorption Fine Structure)方法研究了担载样品的结构.结果显示担载簇与FeCo_3(CO)_(11)PPh_3^-晶体具有相同的结构模式,尤其是膦配体确实与一Co原子相连接.EXAFS结果表明:(1)与FoCo_3(CO)_(12)^-(其簇骼具有三重对称性结构)比较,锚联使Co—Fe键增长0.005nm;金属-金属及金属-桥联碳壳层的Debye-Waller因子均增大约一倍而金属-端联碳壳层的值变化很小.说明金属-金属间实际键长值具有一较宽分布,因而其簇骼已偏离了三重对称结构;(2)与FeCo_3(CO)_(11)PPh_3^-晶体的结构比较.Co—Fe键长长0.003nm.而Co—Co键长则短约0.002nm.考虑到EXAFS分析只能给出平均键长值,因此认为,存在于FeCo_3(CO)_(11)PPh_3^-晶体中的由于一个羰基被膦配体取代而引起的簇骼畸变,在锚联后被加剧.
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.
