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首页> 外文期刊>Chemistry: A European journal >Selective Ring-Opening Reactions of [1]Ferrocenophanes with Boron Halides: A Novel Route to Functionalized Ferrocenylboranes and Boron-Containing Oligo-and Poly(ferrocene)s
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Selective Ring-Opening Reactions of [1]Ferrocenophanes with Boron Halides: A Novel Route to Functionalized Ferrocenylboranes and Boron-Containing Oligo-and Poly(ferrocene)s

机译：[1]铁茂铁与卤化硼的选择性开环反应：一种功能化的二茂铁硼烷和含硼的寡聚和二茂铁的新途径

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摘要

The reavtivity of strained [1]ferrocenophanes, [Fe(#eta#-C_5H+4)_2ER_x] (ER_x=SiMe_2, 1a; SiMePh, 1b; SnR_2, 1c), towards boron halides has been investigated and has been shown to provide a facile pathway to ferrocene derivatives functionalized with Lewis acidic boron centers. The boron halides RBX_2 (R = Cl, Ph, fc; X = Cl, Br) (fc = Fe(#eta#-C_5H_4)_2) lead ot selective cleavage of the Si-Cp bonds in 1a and 1b to give, depending on the reaction stoichiometry, functionalized mono-or dierrocenylboranes R_nB(#eta#-C_5H_4)Fe(#eta#-C_6H_4Si-Me_2Cl)]_(3-n) (2a:R = Cl, n = 2; 2b : R = Cl, n = 1; 2c: R = Ph, n = 10 and R_nB[(#eta#-C_5H_4SiMePhCl)]_(3-n) (2d: R = Cl, n = 2) in high yields. Compound 2a-d were characterized by multinuclear NMR spectroscopy, mass spectrometry, and by single-crystal X-ray diffraction (for 2b). Most likely due to steric constraints, a triferrocenylborane was not obtained even from the reaction of BCl_3 with an excess of 1a, whereas facile formation of the diferrocenylphenylborane 2c from PhBCl_2 adn two equivalents of 1a was observed. Selective hydrolysis of the B-Cl bonds of chlorodiferrocenylborane 2b in the presence of trace amounts of water led to the silylated tetranuclear ferrocene complex [(ClMe_2Sifc)_2B-O-B(fcSiMe_2Cl)_2] (3) without cleavage of the Si-Cl bonds. The structure of 3 was confiremd by an X-ray diffraction study. Studies of the reactivity of the higher Group 14 homologue of 1a and 1b, the tin-bridged [1]ferrocenophane 1c, revealed that facile addition of B-Cl bonds occurs across the Sn-Cp bonds to yield the 1-stannyl-1'-borylferrocenes [(ClMes_2Sn)fc(BClR)] (4a: R = Cl; 4b: R = Ph; Mes = 2, 4, 6-Me_3C_6H_2). The new syntehtic methodology can be extended to bifunctional Lewis acids such as the bis(boryl)ferrocene 1,1'-fc(BBr_2)_2, which affords the linear boron-bridged ferrocene trimer 1,1'-[fc{B9Br)fcSiMe_2Br}_2 5 in 54% isolated yiled. In order to incorporate the functionalized ferrocenylboranes into polymer structures, compounds 2c was reduced with Li[BEt_3H] to give the silicon-hydride functionalized specues [PhB(#eta#-C_5H_4)Fe(#eta#-C_5H_4SiMe_2H)}_2] (6), which was then used as a capping reagent in the transition metal catalyzed polymerization of 1a. This process leads to the incorporation of the ferrocenyl-borane unit into the main chain of poly(ferrocenylsilane) to afford [PhB-{(fcSiMe_2)(n-1)fcSiMe_2H}_2] (7).
机译：已研究了应变的[1]二茂铁蛋白[Fe（＃eta＃-C_5H + 4）_2ER_x]（ER_x = SiMe_2，1a; SiMePh，1b; SnR_2，1c）对卤化硼的反渗透性。一种容易被路易斯酸性硼中心官能化的二茂铁衍生物的途径。卤化硼RBX_2（R = Cl，Ph，fc; X = Cl，Br）（fc = Fe（＃eta＃-C_5H_4）_2）导致1a和1b中Si-Cp键的选择性裂解，取决于反应化学计量上，官能化的单或二茂铁基硼烷R_nB（＃eta＃-C_5H_4）Fe（＃eta＃-C_6H_4Si-Me_2Cl）] _（3-n）（2a：R = Cl，n = 2; 2b：R = Cl，n = 1; 2c：R = Ph，n = 10且R_nB [（＃eta＃-C_5H_4SiMePhCl）] _（3-n）（2d：R = Cl，n = 2），产率高。化合物2a- d的特征在于多核NMR光谱，质谱和单晶X射线衍射（针对2b），最有可能由于空间限制，即使BCl_3与过量1a的反应也无法获得三铁茂铁硼烷。从PhBCl_2和两个当量的1a容易地形成二茂铁基苯基硼烷2c。在微量水存在下氯二茂铁基硼烷2b的B-Cl键选择性水解导致甲硅烷基化四核二茂铁络合物[（ClMe_2Sifc）_2B-OB（ fcSiMe_2Cl）_2]（3）w Si-Cl键不断裂。 X射线衍射研究证实了3的结构。对较高的14a族1a和1b（锡桥[1]二茂铁en烷1c）的反应性的研究表明，在Sn-Cp键之间容易形成B-Cl键，从而生成1-stannyl-1' -硼基二茂铁[[ClMes_2Sn）fc（BClR）]（4a：R ＝ Cl; 4b：R ＝ Ph; Mes ＝ 2、4、6-Me_3C_6H_2）。新的合成方法可扩展到双官能路易斯酸，例如双（硼基）二茂铁1,1'-fc（BBr_2）_2，可提供线性硼桥联二茂铁三聚体1,1'-[fc {B9Br）fcSiMe_2Br } _2，每54％的受访者中有yield。为了将官能化的二茂铁基硼烷掺入聚合物结构中，用Li [BEt_3H]还原化合物2c，得到氢化硅官能化的化合物[PhB（＃eta＃-C_5H_4）Fe（＃eta＃-C_5H_4SiMe_2H）} _ 2]（6 ），然后在1a的过渡金属催化的聚合反应中用作封端剂。该过程导致将二茂铁基-硼烷单元结合到聚二茂铁基硅烷的主链中，从而提供[PhB-{（fcSiMe_2）（n-1）fcSiMe_2H} _2]（7）。

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