Stíbr Bohumil, Holub Josef, Bakardjiev Mario, Pavlík Ivan, Tok Oleg L, Císarová Ivana, Wrackmeyer Bernd, Herberhold Max
Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic Research Center for New Inorganic Compounds and Advanced Materials, University of Pardubice 250 68, Rez, Czech Republic.
Chemistry. 2003 May 23;9(10):2239-44. doi: 10.1002/chem.200204704.
The reaction of nido-[7,8,9-PC(2)B(8)H(11)] (1) with [CpFe(CO)(2)] (Cp=eta(5)-C(5)H(5) (-)) in benzene (reflux, 3 days) gave an eta(1)-bonded complex [7-Fp-(eta(1)-nido-7,8,9,-PC(2)B(8)H(10))] (2; Fp=CpFe(CO)(2); yield 38 %). A similar reaction at elevated temperatures (xylene, reflux 24 h) gave the isomeric complex [7-Fp-(eta(1)-nido-7,9,10-PC(2)B(8)H(10))] (3; yield 28 %) together with the fully sandwiched complexes [1-Cp-closo-1,2,4,5-FePC(2)B(8)H(10)] 4 a (yield 30%) and [1-Cp-closo-1,2,4,8-FePC(2)B(8)H(10)] 4 b (yield 5%). Compounds 2 and 3 are isolable intermediates along the full eta(5)-complexation pathway of the phosphadicarbaborane cage; their heating (xylene, reflux, 24 h) leads finally to the isolation of compounds 4 a (yields 46 and 52%, respectively) and 4 b (yields 4 and 5%, respectively). Moreover, compound 3 is isolated as a side product from the heating of 2 (yield 10%). The structure of compound 4 a was determined by an X-ray structural analysis and the constitution of all compounds is consistent with the results of mass spectrometry and IR spectroscopy. Multinuclear ((1)H, (11)B, (31)P, and (13)C), two-dimensional [(11)B-(11)B]-COSY, and (1)H[(11)B(selective)] magnetic resonance measurements led to complete assignments of all resonances and are in excellent agreement with the structures proposed.
巢式-[7,8,9-PC(2)B(8)H(11)]（1）与[CpFe(CO)(2)]（Cp = η(5)-C(5)H(5)(-))在苯中（回流，3天）反应，得到η(1)-键合配合物[7-Fp-(η(1)-巢式-7,8,9,-PC(2)B(8)H(10))]（2；Fp = CpFe(CO)(2)；产率38%）。在高温下（二甲苯，回流24小时）进行类似反应，得到异构体配合物[7-Fp-(η(1)-巢式-7,9,10-PC(2)B(8)H(10))]（3；产率28%）以及完全夹心的配合物[1-Cp-闭式-1,2,4,5-FePC(2)B(8)H(10)] 4a（产率30%）和[1-Cp-闭式-1,2,4,8-FePC(2)B(8)H(10)] 4b（产率5%）。化合物2和3是磷二碳硼烷笼沿着完全η(5)-络合途径的可分离中间体；它们加热（二甲苯，回流，24小时）最终得到化合物4a（产率分别为46%和52%）和4b（产率分别为4%和5%）。此外，化合物3是在加热2时作为副产物分离得到的（产率10%）。通过X射线结构分析确定了化合物4a的结构，所有化合物的组成与质谱和红外光谱结果一致。多核（(1)H、(11)B、(31)P和(13)C）、二维[(11)B-(11)B]-COSY以及(1)H[(11)B(选择性)]磁共振测量实现了所有共振的完全归属，并且与所提出的结构非常吻合。
