Formation of Stable trans-Dihydride Ruthenium(II) and 16-Electron Ruthenium(0) Complexes Based on Phosphinite PONOP Pincer Ligands. Reactivity toward Water and Electrophiles
Formation of Stable trans-Dihydride Ruthenium(II) and 16-Electron Ruthenium(0) Complexes Based on Phosphinite PONOP Pincer Ligands. Reactivity toward Water and Electrophiles
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DOI：
10.1021/om9004077
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发表时间：
2009-08-24
期刊：
影响因子：
2.8
通讯作者：
Milstein, David
中科院分区：
文献类型：
--
作者：
Salem, Hiyam;Shimon, Linda J. W.;Milstein, David
合成了一系列基于新的PONOP配体1和10(C5H3N-1，3-(OPR2)(2)：1，R=Pr-I；10，R=Bu-t)的新型Ru配合物，包括稳定的反式二氢化合物(Pr-i-PONOP)Ru(H)(2)(PPh3)(4)和(Bu-t-PONOP)Ru(H)(2)(CO)(12)和稳定的Ru(0)配合物(R-PONOP)Ru(CO)(2)(6，R=Pr-I)；15，R=Bu-t)。用KO‘Bu对12进行去质子化，得到了稳定的16电子Ru(0)络合物(13)。配合物13与H-2反应生成顺式二氢化合物12A，后者异构化为反式二氢化合物12。配合物13与CO反应得到饱和的Ru(0)配合物15。配合物12与水反应导致亚膦配体PONOP的水解和重排生成二聚体(14)。反式二氢化合物4与亲电试剂PhCOCl、Met和MeOTf反应，抽离其中一个氢化物配体，与苯甲醛反应生成单氢化合物(Pr-i-PONOP)Ru(H)(PPh3)(X)(X=Cl(2)，1(8a)，OTf(8b))。类似地，12得到单氢化合物(Bu-t-PONOP)Ru(H)(CO)(X)(X=Cl(11)，OTf(17)，I(18))。Ru(0)络合物6和15与水反应产生O-P键，形成两性离子络合物7和16。用MeOTf或MeI处理2和11导致氯配体的抽离，而不是氢化物，分别形成络合物8a，b和17，18。还介绍了基于配体1和10的其他配合物的合成。
The synthesis of a series of new ruthenium complexes based on the new PONOP ligands 1 and 10 ((C5H3N-1,3-(OPR2)(2): 1, R = Pr-i; 10, R = Bu-t) is presented, including the stable trans-dihydride complexes (Pr-i-PONOP)Ru(H)(2)(PPh3) (4) and (Bu-t-PONOP)Ru(H)(2)(CO) (12) and the stable Ru(0) complexes (R-PONOP)Ru(CO)(2) (6, R = Pr-i; 15, R = Bu-t). A surprisingly stable 16-electron Ru(0) complex (13) was formed by deprotonation of 12 with KO'Bu. Complex 13 reacts with H-2 to afford the cis-dihydride complex 12a, which isomerized to the trans-dihydride 12. Complex 13 reacted with CO to afford the saturated Ru(0) complex 15. Reaction of complex 12 with water led to hydrolysis of the phosphinite PONOP ligand and rearrangement to a dimeric product (14). Reaction of the trans-dihydride complex 4 with the electrophiles PhCOCl, Met, and MeOTf led to abstraction of one of the hydride ligands, forming the monohydride complexes (Pr-i-PONOP)Ru(H)(PPh3)(X) (X = Cl (2), 1 (8a), OTf (8b)) together with benzaldehyde in the case of 2. Similarly, 12 afforded the monohydride complexes (Bu-t-PONOP)Ru(H)(CO)(X) (X = Cl (11), OTf (17), I (18)). Reaction of the Ru(0) complexes 6 and 15 with water resulted in hydrolysis of the O-P bond and formation of the zwitterionic complexes 7 and 16. Treatment of 2 and 11 with MeOTf or MeI resulted in abstraction of the chloride ligand rather than the hydride, forming complexes 8a,b and 17, 18, respectively. Additional syntheses of complexes based on ligands 1 and 10 are presented.