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Gold Complexes with ADAP Ligands: Effect of Bulkiness in Catalytic Carbene Transfer Reactions (ADAP = Alkoxydiaminophosphine)
Organometallics ( IF 2.5 ) Pub Date : 2020-06-19 , DOI: 10.1021/acs.organomet.0c00343 Juan Diego Pizarro 1 , Francisco Molina 1 , Manuel R. Fructos 1 , Pedro J. Pérez 1
Organometallics ( IF 2.5 ) Pub Date : 2020-06-19 , DOI: 10.1021/acs.organomet.0c00343 Juan Diego Pizarro 1 , Francisco Molina 1 , Manuel R. Fructos 1 , Pedro J. Pérez 1
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A family of gold(I) complexes of composition AuCl(ADAP) (ADAP = alkoxydiaminophosphine) has been synthetized through a one-pot simple protocol in which the ADAP ligand is prepared in situ before reaction with the Au(I) source. Structural data demonstrate that these ADAP ligands exert a trans effect superior to those of phosphine or phosphite ligands. Evaluation of the buried volume (%VBur) indicates a steric hindrance higher than those of several NHC, PR3, and P(OR3) ligands, in the context of AuCl(L) complexes. These complexes promote the catalytic transfer of a carbene group from ethyl diazoacetate to alkenes and alkanes. In the case of styrene, both the Csp2–H bonds and the C═C bond are functionalized, the relative ratio depending on the catalyst employed and correlating well with the %VBur value. Data available allow proposing that these compounds display quite similar electronic properties but differ in steric properties, a variable that can be readily controlled upon modifying the alkoxy group at the ADAP ligand by simply replacing the starting alcohol employed in the synthesis.
中文翻译：
具有ADAP配体的金配合物：疏松度对催化碳转移反应的影响（ADAP =烷氧基二氨基膦）
已经通过一锅简单方案合成了组成为AuCl（ADAP）（ADAP =烷氧基二氨基膦）的金（I）配合物家族，其中在与Au（I）源反应之前就地制备了ADAP配体。结构数据表明，这些ADAP配体具有优于膦或亚磷酸酯配体的反式作用。在AuCl（L）络合物的情况下，对掩埋体积（％V Bur）的评估表明，其位阻高于几种NHC，PR 3和P（OR 3）配体。这些络合物促进卡宾基团从重氮乙酸乙酯转移到烯烃和烷烃的催化转移。对于苯乙烯，C sp 2-H键和C═C键已被官能化，相对比例取决于所用催化剂，并且与％V Bur值密切相关。可用数据表明这些化合物显示出非常相似的电子性质，但空间性质不同，该变量可通过简单地替换合成中所用的起始醇来修饰ADAP配体上的烷氧基而容易地控制。
更新日期：2020-07-13
中文翻译：
具有ADAP配体的金配合物：疏松度对催化碳转移反应的影响（ADAP =烷氧基二氨基膦）
已经通过一锅简单方案合成了组成为AuCl（ADAP）（ADAP =烷氧基二氨基膦）的金（I）配合物家族，其中在与Au（I）源反应之前就地制备了ADAP配体。结构数据表明，这些ADAP配体具有优于膦或亚磷酸酯配体的反式作用。在AuCl（L）络合物的情况下，对掩埋体积（％V Bur）的评估表明，其位阻高于几种NHC，PR 3和P（OR 3）配体。这些络合物促进卡宾基团从重氮乙酸乙酯转移到烯烃和烷烃的催化转移。对于苯乙烯，C sp 2-H键和C═C键已被官能化，相对比例取决于所用催化剂，并且与％V Bur值密切相关。可用数据表明这些化合物显示出非常相似的电子性质，但空间性质不同，该变量可通过简单地替换合成中所用的起始醇来修饰ADAP配体上的烷氧基而容易地控制。
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