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Strained Ruthenium Complexes Bearing Tridentate Guanidine-Derived Ligands
Helvetica Chimica Acta ( IF 1.5 ) Pub Date : 2021-05-04 , DOI: 10.1002/hlca.202100044
Daniel Carmona 1 , Eden-Taylor Wilkinson 2 , Fernando Viguri 2 , Ricardo Rodríguez 2 , José A. López 2 , Pilar García-Orduña 2 , Fernando J. Lahoz 2 , Pilar Lamata 2
Affiliation  

The dimer [{(η6-p-cymene)RuCl}2(μ-Cl)2] (cymene=MeC6H4iPr) reacts with N,N′-bis(p-tolyl)-N′′-(2-pyridinylmethyl)guanidine (H2L1) and N,N′-bis(p-tolyl)-N′′-(2-diphenylphosphanoethyl)guanidine (H2L2), in the presence of NaSbF6, giving rise to chlorido compounds of formula [(η6-p-cymene)RuCl(H2L)][SbF6] (H2L=H2L1 (1), H2L2 (2)) in which the guanidine ligand adopts a κ2 chelate coordination mode. The related ligand (S)-N,N′-bis(p-tolyl)-N′′-(1-isopropyl, 2-diphenylphosphano ethyl)guanidine (H2L3) affords mixtures of the corresponding chlorido compound [(η6-p-cymene)RuCl(H2L3)][SbF6] (3) together with the complexes [(η6-p-cymene)RuCl2(H3L3)][SbF6] (4) and [(η6-p-cymene)Ru(κ3N,N′,P-HL3)][SbF6] (10) which contain phosphano-guanidinium and phosphano-guanidinate ions acting as monodentate and tridentate ligand, respectively. Compounds 1, 2 and mixture of 3/4/10 react with AgSbF6 rendering the cationic aqua-complexes [(η6-p-cymene)Ru(H2L)(OH2)][SbF6]2 (H2L=H2L1 (5), H2L2 (6), H2L3 (7)). These aqua-complexes exhibit a temperature-dependent fluxional process in solution. Experimental NMR studies and DFT theoretical calculations on complex 6 suggest that the process involves the exchange between two rotamers around one of the C−N guanidine bonds. Treatment of 57 with NaHCO3 renders the complexes [(η6-p-cymene)Ru(κ3N,N′,N′′-HL1)][SbF6] (8) and [(η6-p-cymene)Ru(κ3N,N′,P-HL)][SbF6] (HL=HL2 (9), HL3 (10)), respectively, in which the HL ligand adopts a fac κ3 coordination mode. The new complexes have been characterized by analytical and spectroscopic means, including the determination of the crystal structures of the compounds 1, 2, 5, 9 and 10, by X-ray diffractometric methods.

中文翻译:

带有三齿胍衍生配体的应变钌配合物

二聚体 [{(η 6 - p -cymene)RuCl} 2 ( μ -Cl) 2 ] (cymene=MeC 6 H 4 i Pr) 与N反应,N' -bis( p -tolyl)- N'' - (2-吡啶基甲基)胍 ( H 2 L1 ) 和N , N' -双(甲苯基)- N'' -(2-二苯基膦乙基)胍 ( H 2 L2 ),在 NaSbF 6存在下,产生式 [(η 6 -p- cymene)RuCl( H 2 L )][SbF 6 ] ( H 2 L = H 2 L1 ( 1 ), H 2 L2 ( 2 )) 其中胍配体采用κ 2螯合配位模式。相关配体 ( S )- N , N' -双(甲苯基)- N'' -(1-异丙基, 2-二苯基膦乙基)胍 ( H 2 L3 ) 提供相应氯代化合物 [(η 6 - p-cymene)RuCl( H 2 L3 )][SbF 6 ] ( 3 ) 连同配合物 [(η 6 - p -cymene)RuCl 2 ( H 3 L3 )][SbF 6 ] ( 4 ) 和 [(η 6 ) - p -cymene)Ru(κ 3 N , N' , P- HL3 )][SbF 6 ] ( 10 ),其包含分别作为单齿和三齿配体的膦酰胍和膦酰胍离子。化合物12和的混合物3 / 4 / 10与 AgSbF 6反应生成阳离子水络合物 [(η 6 - p -cymene)Ru( H 2 L )(OH 2 )][SbF 6 ] 2 ( H 2 L = H 2 L1 ( 5 )、H 2 L2 ( 6 )、H 2 L3 ( 7 ))。这些水复合物在溶液中表现出依赖于温度的流动过程。复杂的核磁共振实验研究和 DFT 理论计算图 6表明该过程涉及围绕 CN 胍键之一的两个旋转异构体之间的交换。用 NaHCO 3处理57产生复合物 [(η 6 - p -cymene)Ru(κ 3 N , N' , N'' - HL1 )][SbF 6 ] ( 8 ) 和 [(η 6 - p -cymene)Ru(κ 3 N , N' , P- HL )][SbF 6 ] ( HL = HL2 ( 9 ), HL3( 10 )),其中HL配体采用fac κ 3配位模式。新的配合物已经被表征通过分析和光谱手段,包括确定化合物的晶体结构的125910,通过X射线衍射物的方法。
更新日期:2021-06-15
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