Scheer Manfred, Gregoriades Laurence J, Zabel Manfred, Bai Junfeng, Krossing Ingo, Brunklaus Gunther, Eckert Hellmut
Institut für Anorganische Chemie der Universität, Regensburg, 93040 Regensburg, Germany.
Chemistry. 2008;14(1):282-95. doi: 10.1002/chem.200700715.
Reaction of complex [Cp2Mo2(CO)4(micro,eta 2-P2)] (Cp=C5H5 (1)) with CuPF6, AgX (X=BF4, ClO4, PF6, SbF6, Al{OC(CF3)3}4) and [(Ph3P)Au(THF)][PF6] (THF=tetrahydrofuran), respectively, results in the facile formation of the dimers 3 b-h of the general formula [M2({Cp2Mo2 (CO)4(micro,eta 2:eta 2-P2)}2)({Cp2Mo2(CO)4 (micro,eta 2:eta 1:eta 1-P2)}2)][X]2 (M=Cu, Ag, Au; X=BF4, ClO4, PF6, SbF6, Al{OC(CF3)3}4). As revealed by X-ray crystallography, all these dimers comprise dicationic moieties that are well-separated from the weakly coordinating anions in the solid state. If 1 is allowed to react with AgNO2 and LAuCl (L=CO or tetrahydrothiophene), respectively, the dimer [Ag2{Cp2Mo2 (CO)4(micro,eta 2:eta 1:eta 1-P2)}2(eta 2-NO2)2] (5) and the complex [AuCl{Cp2Mo2(CO)4(micro,eta 2:eta 1-P2)}] (6) are formed, which have also been characterised by X-ray crystallography. In compounds 5 and 6, the anions remain coordinated to the Group 11 metal centres. Spectroscopic data suggest that the dimers 3 b-h display dynamic behaviour in solution and this is discussed by using the comprehensive results obtained for 3 g (M=Ag; X=Al{OC(CF3)3}4) as a basis. The interpretation of the experimental results is facilitated by density functional theory (DFT) calculations on 3 g (structures, energetics, NMR shielding tensors). The 31P magic angle spinning (MAS) NMR spectra recorded for the dimers 3 b (M=Cu; X=PF6) and 3c (M=Ag; X=BF4) as well as that of the previously reported one-dimensional (1 D) polymer [Ag2{Cp2Mo2(CO)4(micro,eta 2:eta 1:eta 1-P2)}3(micro,eta 1:eta 1-NO3)]n[NO3]n (4) are also discussed herein and the strong dependence of the chemical shift of the phosphorus atoms within each compound on subtle structural differences in the solid state is demonstrated. Furthermore, the X-ray crystallographic and 31P MAS NMR spectroscopic characterisation of a new polymorph of 1 is reported.
配合物[Cp2Mo2(CO)4(μ,η2 - P2)]（Cp = C5H5 (1)）分别与CuPF6、AgX（X = BF4、ClO4、PF6、SbF6、Al{OC(CF3)3}4）以及[(Ph3P)Au(THF)][PF6]（THF = 四氢呋喃）反应，可轻松形成通式为[M2({Cp2Mo2(CO)4(μ,η2:η2 - P2)}2)({Cp2Mo2(CO)4(μ,η2:η1:η1 - P2)}2)][X]2的二聚体3 b - h（M = Cu、Ag、Au；X = BF4、ClO4、PF6、SbF6、Al{OC(CF3)3}4）。X射线晶体学研究表明，所有这些二聚体均包含双阳离子部分，在固态时它们与弱配位阴离子分隔良好。若让1分别与AgNO2和LAuCl（L = CO或四氢噻吩）反应，则会形成二聚体[Ag2{Cp2Mo2(CO)4(μ,η2:η1:η1 - P2)}2(η2 - NO2)2]（5）和配合物[AuCl{Cp2Mo2(CO)4(μ,η2:η1 - P2)}]（6），它们也通过X射线晶体学进行了表征。在化合物5和6中，阴离子仍与第11族金属中心配位。光谱数据表明二聚体3 b - h在溶液中表现出动态行为，并以对3 g（M = Ag；X = Al{OC(CF3)3}4）获得的全面结果为基础对此进行了讨论。通过对3 g进行密度泛函理论（DFT）计算（结构、能量、NMR屏蔽张量），有助于对实验结果进行解释。本文还讨论了为二聚体3 b（M = Cu；X = PF6）和3 c（M = Ag；X = BF4）记录的31P魔角旋转（MAS）NMR光谱以及先前报道的一维（1D）聚合物[Ag2{Cp2Mo2(CO)4(μ,η2:η1:η1 - P2)}3(μ,η1:η1 - NO3)]n[NO3]n（4）的光谱，并证明了每种化合物中磷原子化学位移对固态中细微结构差异的强烈依赖性。此外，还报道了1的一种新多晶型物的X射线晶体学和31P MAS NMR光谱表征。
