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“Pincer” Pyridine–Dicarbene–Iridium and ‐Ruthenium Complexes and Derivatives Thereof
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-08-23 , DOI: 10.1002/ejic.202000429 Andreas A. Danopoulos 1 , Pierre Braunstein 2 , Jörg Saßmannshausen 3 , David Pugh 4 , Joseph A. Wright 5
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-08-23 , DOI: 10.1002/ejic.202000429 Andreas A. Danopoulos 1 , Pierre Braunstein 2 , Jörg Saßmannshausen 3 , David Pugh 4 , Joseph A. Wright 5
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The cationic pincer‐type complexes [IrI(CNMeC)L]X {CNMeC = [2,6‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene]‐3,5‐dimethylpyridine, L = CO, X = PF6 4; L = CH3CN, X = PF6 5; L = pyridine, X = BArF4, ArF = 3,5‐bis‐trifluoromethyl‐phenyl 6}, that were obtained from [IrI(CNMeC)Cl] (1) by displacement of the chloride ligand were structurally characterized. Complexes 4 and 5 adopt square planar, in‐plane distorted geometries, and in 6 the metal environment shows substantial pyramidalization. Theoretical calculations of the cations in 4 and 6 reproduce the experimental structures and rationalize their features. 1 undergoes oxidative transformations with CH2Cl2 to cis‐[IrIII(CNMeC)(CH2Cl)Cl2] (7) and with PhICl2 to mer‐[IrIII(CNMeC)Cl3] (8). The ruthenium derivatives trans‐[RuII(CNC)Cl2L] {CNC = [2,6‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene]‐pyridine, L = pyridine, 10} and [RuII(CNC)(η2,η2‐nbd)](X)2 . 2L (nbd = 2,5‐norbornadiene, L = CH3CN, X = BF4 11), were prepared by the reaction of cis‐trans‐[RuCl2(nbd)(py)2] and trans‐cis‐[RuCl2(nbd)(pip)2] (pip = piperidine) with the ligand CNC, respectively; both adopt distorted octahedral structures. The back‐bonding in 11 is comparable to that in its precursor complex, indicating minimal contribution of the NHC donors to this effect. Substitution of both chlorides in the known cis‐[RuII(CNC)Cl2L] (L = PPh3) by azido ligands gave cis‐[RuII(CNC)(N3)2L] (L = PPh3, 12), which by photolytic cleavage of the coordinated N3 failed to produce well‐defined complexes.
中文翻译：
“ Pincer”吡啶-二卡宾-铱和钌络合物及其衍生物
阳离子钳型配合物[Ir I（CN Me C）L] X {CN Me C = [2,6-双（2,6-二异丙基苯基）咪唑-2-亚基] -3,5-二甲基吡啶，L = CO，X = PF 6 4；L = CH 3 CN，X = PF 6 5；L =吡啶，X = BAr F 4，Ar F = 3,5-双三氟甲基-苯基6 }，是通过置换氯配体从[Ir I（CN Me C）Cl]（1）中获得的表征。配合物4和5采用方形平面，面内扭曲几何形状，而在6中金属环境呈显着的金字塔形。4和6中阳离子的理论计算重现了实验结构并使其特征合理化。1层进行氧化，用CH变换2氯2至顺式- [铱III（CN我C）（CH 2 Cl）的氯2 ]（7）中并用PhICl 2至聚体-的[Ir III（CN我C）氯3 ]（8）。钌衍生物反式[Ru II（CNC）氯2 L] {CNC = [2,6-双（2,6-二异丙基苯基）咪唑-2-亚基] -吡啶，L =吡啶，10 }和的[Ru II（CNC）（η 2，η 2 -nbd）]（X）2。2L（nbd = 2,5-降冰片二烯，L = CH 3 CN，X = BF 4 11）是通过顺-反-[RuCl 2（nbd）（py）2 ]和反-顺-[[具有配体CNC的RuCl 2（nbd）（pip）2 ]（pip =哌啶）；两者都采用扭曲的八面体结构。11中的背键与它的前体复合物相当，表明NHC供体对此作用的贡献最小。叠氮基配体将两种氯化物替换为已知的顺式[Ru II（CNC）Cl 2 L]（L = PPh 3）（L = PPh 3，顺式[Ru II（CNC）（N 3）2 L）（L = PPh 3，12），其通过配位N 3的光解裂解未能产生明确的复合物。
更新日期：2020-09-15
中文翻译：
“ Pincer”吡啶-二卡宾-铱和钌络合物及其衍生物
阳离子钳型配合物[Ir I（CN Me C）L] X {CN Me C = [2,6-双（2,6-二异丙基苯基）咪唑-2-亚基] -3,5-二甲基吡啶，L = CO，X = PF 6 4；L = CH 3 CN，X = PF 6 5；L =吡啶，X = BAr F 4，Ar F = 3,5-双三氟甲基-苯基6 }，是通过置换氯配体从[Ir I（CN Me C）Cl]（1）中获得的表征。配合物4和5采用方形平面，面内扭曲几何形状，而在6中金属环境呈显着的金字塔形。4和6中阳离子的理论计算重现了实验结构并使其特征合理化。1层进行氧化，用CH变换2氯2至顺式- [铱III（CN我C）（CH 2 Cl）的氯2 ]（7）中并用PhICl 2至聚体-的[Ir III（CN我C）氯3 ]（8）。钌衍生物反式[Ru II（CNC）氯2 L] {CNC = [2,6-双（2,6-二异丙基苯基）咪唑-2-亚基] -吡啶，L =吡啶，10 }和的[Ru II（CNC）（η 2，η 2 -nbd）]（X）2。2L（nbd = 2,5-降冰片二烯，L = CH 3 CN，X = BF 4 11）是通过顺-反-[RuCl 2（nbd）（py）2 ]和反-顺-[[具有配体CNC的RuCl 2（nbd）（pip）2 ]（pip =哌啶）；两者都采用扭曲的八面体结构。11中的背键与它的前体复合物相当，表明NHC供体对此作用的贡献最小。叠氮基配体将两种氯化物替换为已知的顺式[Ru II（CNC）Cl 2 L]（L = PPh 3）（L = PPh 3，顺式[Ru II（CNC）（N 3）2 L）（L = PPh 3，12），其通过配位N 3的光解裂解未能产生明确的复合物。
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