Synthesis And Crystal Structures Of Iron And Ruthenium Carbonyl Derivatives Containing Bridging Phosphorus And Chlorine Ligands

The reaction of Fe3(CO)12 and Ru3(CO)12 with P(NEt2)2Cl, gave six novel dinuclear and trinuclear iron and ruthenium carbonyl derivatives. The known carbonyl compound II a was also obtained. Their formulas are as follows:Ia Fe2(CO)6(μ-Cl) [μ-P(NEt2)2]Ib Fe2(CO)6[μ-P (NEt2)2]2Ic Fe3(CO)9(μ-CO) (μ3-PNEt2)Id Fe3 (CO) 9 (μ 3 - PNEt2) [P (NEt2) 3]IIa HRu3 (CO) 9 {μ 3-η2-P (NEt2) 2}IIb Ru3(CO)7(μ-Cl) 2[ μ- P(NEt2)2] 2These complexes have been characterized by elementary analysis, IR, :HNMR and MS(FD) spectra, the crystal and molecular structures of new clusters were determined by X-ray single crystal diffraction. Crystal data for la: triclinic (PI), a = 0. 8745(6)nm, b= 0. 9601 (7)nm , c =1. 3996 (10)nm, alpha= 74. 131(11)°,beta=79.480(12)° , gamma = 69. 727(12)°, V=1.0553(13)nm3, DC = 1.543g. cm-3, Z = 2 , R = 0. 0443, Rw = 0.0831 . Ib: 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, Rw = 0. 1035 . Ic: Monoclinic (P2, /c), a = 1.0280(5) nm, b = 1. 2113 (5) nra, c = 1.7192 (7)nm, beta= 93. 560(7)°,V = 2. 1366 (16) nm3, DC = 1. 712 g. cm-3, Z = 4, R=0. 0577, Rw=0. 1187. Id : mono-clinic (Cc) ,a = 1. 5875(7)nm, b = 1. 0359 (5) nm, c = 2. 1919 (9) nm, 3=101.266 (8) , V = 3. 535(3)nm3, DC = 1. 443g. cm-3, Z = 4, R=0. 0742, Rw=0. 1385. lib: triclinic( Pi), a = 1. 2879(6)nm, b = 1.6539(8)nm, c = 1.6436(8)nm, P = 95. 786 (7)° , V = 3. 483 (3) nm3, DC = 1. 756 g. cm-3, Z= 4, R=0. 0550, Rw=0. 1332. The structures of them are shown as follows:During the reactions, 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 and ruthenium atoms to form the clusters as listed above. la and Ib are diiron carbonyl clusters containing double bridging ligands. Ic and Id are triiron carbonyl clusters containing face-bridging PR(R=NEt2) ligand. The different of Ic and Id are Ic has a bridging carbonyl ligand and Id has an ending PR3 ligand. Cluster lib has a triangle Ru3 framework. Two Ru~Ru bonds are supported by @-PR2, the other one is connected by double Cl bridges.