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首页> 外文期刊>Chemistry: A European journal >Activation of Strong Boron-Fluorine and Silicon-Fluorine sigma-Bonds: Theoretical Understanding and Prediction
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Activation of Strong Boron-Fluorine and Silicon-Fluorine sigma-Bonds: Theoretical Understanding and Prediction

机译：硼氟和硅氟西格玛键的活化：理论理解和预测

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摘要

The oxidative addition of BF3 to a platinum(0) bis(phosphine) complex [Pt(PMe3)(2)] (1) was investigated by density functional calculations. Both the cis and trans pathways for the oxidative addition of BF3 to 1 are endergonic (G degrees=26.8 and 35.7kcalmol(-1), respectively) and require large Gibbs activation energies (G degrees=56.3 and 38.9kcalmol(-1), respectively). A second borane plays crucial roles in accelerating the activation; the trans oxidative addition of BF3 to 1 in the presence of a second BF3 molecule occurs with G degrees and G degrees values of 10.1 and -4.7kcalmol(-1), respectively. G degrees becomes very small and G degrees becomes negative. A charge transfer (CT), FBF3, occurs from the dissociating fluoride to the second non-coordinated BF3. This CT interaction stabilizes both the transition state and the product. The BF sigma-bond cleavage of BF2ArF (Ar-F=3,5-bis(trifluoromethyl)phenyl) and the BCl sigma-bond cleavage of BCl3 by 1 are accelerated by the participation of the second borane. The calculations predict that trans oxidative addition of SiF4 to 1 easily occurs in the presence of a second SiF4 molecule via the formation of a hypervalent Si species.
机译：通过密度泛函计算研究了BF3在铂（0）双（膦）配合物[Pt（PMe3）（2）]（1）中的氧化加成反应。 BF3氧化成1的顺式和反式途径都是二十碳五烯酸（分别为G度= 26.8和35.7kcalmol（-1）），并且需要较大的吉布斯活化能（G度= 56.3和38.9kcalmol（-1）），分别）。第二个硼烷在加速活化中起关键作用。在第二个BF3分子存在的情况下，BF3的反氧化加成反应的G度和G度值分别为10.1和-4.7kcalmol（-1）。 G度变得非常小，G度变为负。从离解的氟化物到第二个非配位的BF3发生电荷转移（CT）FBF3。这种CT相互作用可稳定过渡态和产物。 BF2ArF（Ar-F = 3,5-双（三氟甲基）苯基）的BFσ键断裂和BCl3的BClσ键断裂通过第二硼烷的参与而加速。该计算预测SiF4向1的反式氧化加成容易在第二SiF4分子存在下通过形成高价Si物质而发生。

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