Tetrahedral Gold(I) Clusters with Carba-closo-dodecaboranylethynido Ligands: [{12-(R3PAu)2CC-closo-1-CB11H11}2]
作者:Alexander Himmelspach、Maik Finze、Stephan Raub
DOI:10.1002/anie.201007239
日期:2011.3.7
the solid state and in solution, the neutral dinuclear gold(I) complexes [12‐(R3PAu)2CC‐closo‐1‐CB11H11] (R=Me, Et) dimerize to tetranuclear gold(I) clusters held together by aurophilic interactions. For the Et3P complex, the dimer and the monomer exist in equilibrium in solution at 25 °C. In contrast, even at 75 °C only dimers (AuI4 clusters), are observed for the Me3P complex (see structure: C black
Neutral R
<sub>3</sub>
PAuGe
<sub>9</sub>
(Hyp)
<sub>3</sub>
(R=Et,
<sup>
<i>n</i>
</sup>
Pr,
<sup>
<i>i</i>
</sup>
Pr,
<sup>
<i>n</i>
</sup>
Bu,
<sup>
<i>t</i>
</sup>
Bu, Cy) (Hyp=Si(SiMe
<sub>3</sub>
) Clusters give new insights into the ligand strength of the metalloid [Ge
<sub>9</sub>
(Hyp)
<sub>3</sub>
]
<sup>−</sup>
cluster
作者:Christian Gienger、Andreas Schnepf
DOI:10.1002/zaac.202100093
日期:2021.9.27
We present new insights into the ligand strength of the metalloid [Ge9(Hyp)3]− cluster (Hyp=Si(SiMe3)3) alongside novel neutral Ge9clusters of the composition R3PAuGe9(Hyp)3 (R=Et, nPr, iPr, nBu, tBu, Cy). These clusters are synthesized in good yields from KGe9(Hyp)3 and R3PAuCl. Further experiments with these new clusters show that the ligand strength of [Ge9(Hyp)3]− is in between aryl and alkyl phosphines
我们本新的见解准金属的配位体强度[葛9脯氨酸(Hyp)3 ] -簇脯氨酸(Hyp = SI(森达3)3)并排新颖中性葛9组合物R的簇3 PAuGe 9脯氨酸(Hyp)3(R =Et, n Pr, i Pr, n Bu, t Bu, Cy)。这些簇是由 KGe 9 (Hyp) 3和 R 3 PAuCl以良好的产率合成的。这些新簇的进一步实验表明 [Ge 9 (Hyp) 3 ]的配体强度-介于芳基膦和烷基膦之间。
The occurrence of direct transmetalation between gold(III) and boron species during gold-catalyzed cross-coupling reactions has recently become the subject of intense discussion. In this work, we investigate the transmetalation reaction between discrete, stable gold(III) complexes and boron reagents. Interestingly, electron-rich arylboronic acids remain unreactive under neutral conditions, whereas
Experimental Evaluation of (L)Au Electron‐Donor Ability in Cationic Gold Carbene Complexes
作者:Robert G. Carden、Nathan Lam、Ross A. Widenhoefer
DOI:10.1002/chem.201703820
日期:2017.12.19
more inductively electron donating and are comparable π‐donors and for this reason, the extent of (L)Au→C1 electron donation in gold carbene complexes appears to exceed that provided by a p‐(dimethyamino)phenyl group. Furthermore, the [L=P(tBu)2o‐biphenyl]Au fragment is a nominally stronger electron donor than the (IPr)Au fragment, and both are significantly more inductively electron donating than the
29 Si NMR光谱用于评估阳离子金(β,β-二甲硅烷基)亚乙烯基络合物[(L)Au = C = CSi(Me)2 CH 2 CH 2 Si(ME)2 ] + B(C 6 ˚F 5)4 - [L = P(吨丁基)2 ø -联苯或NHC]相对于p取代的芳基中的α-芳基- (β,β-二甲硅烷基)乙烯基阳离子[(p- C 6 H 4 X)-C = CSi(Me)2 CH 2 CH 2的Si(Me)的2 ] + B(C 6 ˚F 5)4 - 。同样,采用19 F NMR评估中性金氟苯基络合物(L)Au(C 6 H 4 F)和阳离子(氟苯基)甲氧基卡宾中(L)Au片段的σ-和π-电子供体性质相对于质子化单氟二苯甲酮的对位取代芳基[[(L)AuC(OMe)(C 6 H 4 F)] + SbF 6 − [L = P(t Bu)2 o-联苯或IPr] p‐C 6 H 4 X)(C 6 H 4 F)COH]
A silver-free system for the direct C–H auration of arenes and heteroarenes from gold chloride complexes
作者:Nanna Ahlsten、Gregory J. P. Perry、Xacobe C. Cambeiro、Tanya C. Boorman、Igor Larrosa
DOI:10.1039/c3cy00240c
日期:——
A new methodology for the direct CâH auration of electron-deficient arenes and heteroarenes with simple bases and readily available [Au(PR3)Cl] complexes is described. This system allows the preparation of a wide scope of arylâAu(I) compounds without the need for using Ag(I) additives or preparing and isolating basic Au(I) hydroxide complexes.