Fe3(CO)12与P(NEt2)2Cl的反应--两核和三核铁羰基簇合衍生物的合成和晶体结构

Fe_3(CO)_(12)与配位基前体P(NEt_2)_2Cl反应,给出4个新的两核和三核铁羰基簇合衍生物:Fe_2(CO)_6(μ-Cl)μ-P(NEt_2)_2](Ⅰ),Fe_2(CO)_6μ-P(NEt_2)_2]_2(Ⅱ),Fe_3(CO)_9(μ-CO)(μ_3-PNEt_2)(Ⅲ)和Fe_3(CO)_9(μ_3-PNEt_2)P(NEt_2)_3](Ⅳ)。在反应期间,配前体分子中的P-Cl和P-N键劈开,形成的分子片Cl、PNEt_2、P(NEt_2)_2和P(NEt_2)_3作为配体与铁羰合物重新组建成上述簇合物。利用X射线衍射法测定了它们的晶体结构。Ⅰ属三斜晶系,P1空间群,晶胞参数a=0.8745(6)nm,b=0.9601(7)nm,c=1.3996(10)nm,α=74.131(11)°,β=79.480(12)°,γ=69.727(12)°,V=1.0553(13)nm~3,D_c=1.543g·cm~(-3),Z=2,R=0.0443,wR=0.0831。Ⅱ属正交晶系,Pbcn空间群,晶胞参数a=1.0153(3)nm,b=1.7543(5)nm,c=1.6860(5)nm,V=3.0031(15)nm~3,D_c=1.394g·cm~(-3),Z=4,R=0.0519,wR=0.1035。Ⅲ属单斜晶系,P2_1/c空间群,晶胞参数a=1.0280(5)nm,b=1.2113(5)nm,c=1.9192(7)nm,β=93.560(7)°,V=2.1366(16)nm~3,D_c=1.712g·cm~(-3),Z=4。Ⅳ属单斜晶系,Cc空间群,晶胞参数a=1.5875(7)nm,b=1.0359(5)nm,C=2.1919(9)nm,β=101.266(8)°,V=3.535(3)nm~3,Dc=1.443g·cm~(-3),Z=4。Ⅰ和Ⅱ为两核铁簇,其簇骨架Fe_2PCl和Fe_2P_2呈蝶状。Ⅲ和Ⅳ

The Reaction of Fe3 (CO)12 with P(NEt2)2Cl-Synthesis and Crystal Structures of Dinuclear and Trinuclear Iron Carbonyl Clusters

The reaction of Fe3(CO)12 with P(NEt2)2Cl, gave four novel dinuclear and trinuclear phosphorus clusters: (Fe2(CO)6(u-Cl)u-P(NEt2)2] ( I), Fe2(CO)6u-P(NEt2)2]2 ( II), Fe3(CO)9(u-CO) (u3-PNEt2) (III) and Fe3 (CO) 9(u3-PNEt2) P(NEt2) 3] (IV). During the reaction, the ligand precursor was cleaved or formed in its P-C1 and P-N bonds to give the fragments Cl, PNEt2, P(NEt2)2 and P(NEt2)3, that coordinated to the iron atoms to form the clusters as listed above. The crystal structures of I ~ IV have been determined by X-ray diffraction. Crystal data for I: triclinic (P1), a =0.8745(6) nm, b=0.9601(7) nm, c = 1.3996(10) nm, a =74. 131 (11), B = 79.480(12), y = 69.727(12), V= 1.0553(13) nm3, Dc = 1.543g.cm-3, Z=2, R =0.0443, wR = 0.0831. Crystal data for II:orthorhombic (Pbcn), a = 1.0153(3) nm, b = 1. 7543(5) nm, c = 1. 6860(5) nm, V = 3. 0031(15) nm3, Dc = 1. 394g ,cm-3, Z = 4, R = 0.0519, wR = 0. 1035. Crystal data for III: Monoclinic (P21/c), a = 1.0280(5) nm, b = 1.2113(5) nm, c = 1. 7192(7) nm, B = 93. 560(7), V = 2. 1366(16) nm3, Dc = 1.712g. cm-3, Z=4. Crystal data for IV: monoclinic (Cc), a = 1. 5875(7) nm, b = 1. 0359(5) nm, c = 2. 1919(9)nm, B= 101. 266(8), V = 3. 535(3)nm3, Dc = 1. 443g.cm-3, Z= 4. I and II are the dinuclear iron clusters. The bridging P and Cl atoms with Fe atoms form respectively a folded Fe2PCl or Fe2P2 core in butterfly shape. III and IV are trinuclear iron clusters , in whish , Fe3P core containing face bridging ligand u3-PNEt2 is triangular pyramid geometry. CCDC: I, 211253; II, 211254;III, 211255; IV, 211252.