The synthesis of new families of stable or at least spectroscopically observable gold(III) hydride complexes is reported, including anionic cis-hydrido chloride, hydrido aryl, and cis-dihydride complexes. Reactions between (C^C)AuCl(PR3) and LiHBEt3 afford the first examples of gold(III) phosphino hydrides (C^C)AuH(PR3) (R = Me, Ph, p-tolyl; C^C = 4,4′-di-tert-butylbiphenyl-2,2′-diyl). The X-ray structure of (C^C)AuH(PMe3) was determined. LiHBEt3 reacts with (C^C)AuCl(py) to give [(C^C)Au(H)Cl]−, whereas (C^C)AuH(PR3) undergoes phosphine displacement, generating the dihydride [(C^C)AuH2]−. Monohydrido complexes hydroaurate dimethylacetylene dicarboxylate to give Z-vinyls. (C^N^C)Au pincer complexes give the first examples of gold(III) bridging hydrides. Stability, reactivity and bonding characteristics of Au(III)–H complexes crucially depend on the interplay between cis and trans-influence. Remarkably, these new gold(III) hydrides extend the range of observed NMR hydride shifts from δ −8.5 to +7 ppm. Relativistic DFT calculations show that the origin of this wide chemical shift variability as a function of the ligands depends on the different ordering and energy gap between “shielding” Au(dπ)-based orbitals and “deshielding” σ(Au–H)-type MOs, which are mixed to some extent upon inclusion of spin–orbit (SO) coupling. The resulting 1H hydride shifts correlate linearly with the DFT optimized Au–H distances and Au–H bond covalency. The effect of cis ligands follows a nearly inverse ordering to that of trans ligands. This study appears to be the first systematic delineation of cis ligand influence on M–H NMR shifts and provides the experimental evidence for the dramatic change of the 1H hydride shifts, including the sign change, upon mutual cis and trans ligand alternation.

中文翻译：

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解锁金 (III) 氢化物中的结构多样性：顺/反对稳定性、插入化学和 NMR 化学位移的意外相互作用

报道了稳定的或至少在光谱上可观察到的金 (III) 氢化物复合物的新家族的合成，包括阴离子顺式氢化氯化物、氢化芳基和顺式二氢化物复合物。(C^C)AuCl(PR3) 和 LiHBEt3 之间的反应提供了金 (III) 膦基氢化物 (C^C)AuH(PR3)（R = Me，Ph，对甲苯基；C^C = 4， 4'-二叔丁基联苯-2,2'-二基)。确定了 (C^C)AuH(PMe3) 的 X 射线结构。LiHBEt3 与 (C^C)AuCl(py) 反应生成 [(C^C)Au(H)Cl]-，而 (C^C)AuH(PR3) 发生膦置换，生成二氢化物 [(C^C) )AuH2]-。一氢化物与氢金酸二甲基乙炔二羧酸盐形成 Z-乙烯基化合物。(C^N^C)Au 钳形配合物给出了金 (III) 桥连氢化物的第一个例子。稳定，Au(III)-H 配合物的反应性和键合特性关键取决于顺式和反式影响之间的相互作用。值得注意的是，这些新的金 (III) 氢化物将观察到的 NMR 氢化物位移范围从 δ -8.5 扩展到 +7 ppm。相对论 DFT 计算表明，作为配体函数的这种广泛的化学位移变化的起源取决于“屏蔽”Au(dπ) 基轨道和“去屏蔽”σ(Au-H) 型之间的不同排序和能隙MO，在包含自旋轨道 (SO) 耦合后在某种程度上混合。由此产生的 1H 氢化物位移与 DFT 优化的 Au-H 距离和 Au-H 键共价呈线性相关。顺式配体的作用与反式配体的作用几乎相反。