Comparing Protonolysis and Transmetalation Reactions: Microcalorimetric Studies of C–AuI Bonds in [AuRL] Complexes,Inorganic Chemistry

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Comparing Protonolysis and Transmetalation Reactions: Microcalorimetric Studies of C–AuI Bonds in [AuRL] Complexes
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-08-14 00:00:00 , DOI: 10.1021/acs.inorgchem.8b01758
María Pérez-Iglesias ₁ , Pablo Espinet ₁ , Juan A. Casares ₁

Affiliation

The protonolysis of C–Au bonds in [AuRL] organometallic complexes has been studied by calorimetry for 12 R groups. The experimental data have been combined with density functional theory calculations to obtain bond dissociation energy (BDE) values. The C–Au BDE values show a good correlation with the corresponding isolobal C–H BDE values. The heat released in the protonolysis of [AuRL] has also been measured for R = Ph and L = P(OPh)₃, PPh₃, PMe₃, PCy₃, and IPr, and these values strongly depend on the trans influence of L because of the mutual destabilization of the L–Au and Au–C bonds. The enthalpies of the transmetalation reaction [AuR(PPh₃)] + SnIBu₃ → [AuI(PPh₃)] + SnRBu₃ for seven R groups have been measured and compared with those of the corresponding [AuR(PPh₃)] protonolysis.

中文翻译：

比较质子分解和金属转移反应：[AuRL]络合物中的C–Au ^I键的量热研究

通过量热法研究了12个R基团在[AuRL]有机金属配合物中C–Au键的质子分解。实验数据已与密度泛函理论计算相结合，以获得键离解能（BDE）值。C–Au BDE值与相应的等高C–H BDE值显示出良好的相关性。还测量了R = Ph和L = P（OPh）₃，PPh ₃，PMe ₃，PCy ₃和IPr在[AuRL]的质子分解过程中释放的热量，这些值在很大程度上取决于L的反式影响因为L–Au和Au–C键相互不稳定。过渡金属化反应的焓[AuR（PPh ₃）] + SnIBu ₃→[AUI（PPH ₃）] + SnRBu ₃七R基团已被测量并与那些相应的[AUR（PPH相比₃）]质子分解。

更新日期：2018-08-14

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