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Coordination Chemistry of Ru(II) Complexes of an Asymmetric Bipyridine Analogue: Synergistic Effects of Supporting Ligand and Coordination Geometry on Reactivities

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Coordination Chemistry of Ru(II) Complexes of an Asymmetric Bipyridine Analogue: Synergistic Effects of Supporting Ligand and Coordination Geometry on Reactivities molecules Article Coordination Chemistry of Ru(II) Complexes of an Asymmetric Bipyridine Analogue: Synergistic Effects of Supporting Ligand and Coordination Geometry on Reactivities Komi Akatsuka, Ryosuke Abe, Tsugiko Takase and Dai Oyama * Cluster of Science and Engineering, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan; [email protected] (K.A.); [email protected] (R.A.); [email protected] (T.T.) * Correspondence: [email protected]; Tel.: +81-24-548-8199 Received: 29 November 2019; Accepted: 17 December 2019; Published: 19 December 2019 Abstract: The reactivities of transition metal coordination compounds are often controlled by the environment around the coordination sphere. For ruthenium(II) complexes, differences in polypyridyl supporting ligands affect some types of reactivity despite identical coordination geometries. To evaluate the synergistic effects of (i) the supporting ligands, and (ii) the coordination geometry, a series of dicarbonyl–ruthenium(II) complexes that contain both asymmetric and symmetric bidentate polypyridyl ligands were synthesized. Molecular structures of the complexes were determined by X-ray crystallography to distinguish their steric configuration. Structural, computational, and electrochemical analysis revealed some differences between the isomers. Photo- and thermal reactions indicated that the reactivities of the complexes were significantly affected by both their structures and the ligands involved. Keywords: bipyridine; phenanthroline; naphthyridine; ruthenium; carbonyl complex; isomerization; crystal structure 1. Introduction Polypyridines with multiple covalently bonded pyridine groups exhibit unique photophysical and redox properties [1,2]. Among the polypyridines, bipyridine analogues play an important role in the formation of various transition metal complexes as bidentate ligands with two nitrogen donor atoms [3]. Bipyridine analogues function not only as supporting ligands for stabilizing metal complexes, but also as electron pool sites. For example, in addition to catalysts for the production of useful resources, such as in multi-electron reductions of carbon dioxide and water–gas shift reactions [4–11], bipyridine analogues are also utilized as photosensitizers [12] and phosphorescence materials [13]. A variety of studies that imparted selectivity to various reactions by strictly controlling the coordination sphere have been reported for many ruthenium complexes. Various molecular structures can be readily designed for a ruthenium center because ruthenium can take various oxidation states and can easily interact with the ligand. These structures include examples where differences in the coordination geometry dramatically changed both the electrical and photochemical properties of the complex, and therefore its catalysis for chemical reactions [14–16]. Many examples of the relationship between the supporting bipyridine ligands and the reactivity of metal complexes are known. For example, the relationship between the number of heteroatoms involved in the supporting ligand and the reactivity of the complex has been reported in a ruthenium complex containing bipyridine analogues [17]. Recently, we reported the synthesis of ruthenium complexes with 2,2’-bipyridine (bpy) and an analogue, the asymmetric bidentate ligand 2-(2-pyridyl)-1,8-naphthyridine (pynp, Chart1). Molecules 2020, 25, 27; doi:10.3390/molecules25010027 www.mdpi.com/journal/molecules Molecules 2020, 25, 27 2 of 16 Molecules 2019, 24, x FOR PEER REVIEW 2 of 16 TheMolecules supporting 2019, 24, x ligands FOR PEER aff REVIEWected the properties of the complexes, and diastereomers with these ligands2 of 16 showed didifferentfferent reactivities reactivities [18 [18].]. As As is the is casethe incase some in ofsome the studiesof the mentionedstudies mentioned above, the above, difference the showed different reactivities [18]. As is the case in some of the studies mentioned above, the differencein reactivities in reactivities based on coordination based on coordination geometry or thegeometry effect of or the the supporting effect of ligandthe supporting on the properties ligand on of difference in reactivities based on coordination geometry or the effect of the supporting ligand on the complexproperties have of the been complex reported have independently, been reported but independently, there are very few but examples there are that very investigated few examples the the properties of the complex have been reported independently, but there are very few examples thatsynergistic investigated effects ofthe both. synergistic In this study, effects we of prepared both. In a seriesthis study, of Ru(II) we complexes prepared (Chart a series2) containing of Ru(II) that investigated the synergistic effects of both. In this study, we prepared a series of2 +Ru(II) complexesthe asymmetric (Chart bidentate 2) containing pynp and the a asymmetric symmetric bidentate bidentate ligand pynp NˆN, and [Ru(pynp)(NˆN)(CO)a symmetric bidentate2] ligand(NˆN =complexesbpy or 1,10-phenanthroline (Chart 2) containing (phen) the asymmetric as a more rigid bidentate ligand, pynp Chart and1), as a asymmetric platform forbidentate investigating ligand N^N, [Ru(pynp)(N^N)(CO)2]2+ (N^N = bpy or 1,10-phenanthroline (phen) as a more rigid ligand, N^N, [Ru(pynp)(N^N)(CO)2]2+ (N^N = bpy or 1,10-phenanthroline (phen) as a more rigid ligand, Chartthese synergistic1), as a platform effects [for19]. investigating In addition tothese characterizing synergistic the effects above [19]. complexes, In addition we performedto characterizing photo- Chart 1), as a platform for investigating these synergistic effects [19]. In addition to characterizing2+ theand above thermal complexes, reactions we on performed the complexes, photo- along and withthermal the reactions bis–pynp on complex the complexes, [Ru(pynp) along2(CO) with2] theas athe reference above complexes, compound. we We performed comprehensively photo- and evaluated thermal reactions the synergistic on the ecomplexes,ffects of the along coordination with the bis–pynp complex [Ru(pynp)2(CO)2]2+ as a reference compound. We comprehensively evaluated the bis–pynp complex [Ru(pynp)2(CO)2]2+ as a reference compound. We comprehensively evaluated the synergisticgeometry and effects supporting of the coordination ligands on the geometry reactivity. and supporting ligands on the reactivity. synergistic effects of the coordination geometry and supporting ligands on the reactivity. Chart 1. Chemical structures of pynp, bpy, and phen. Chart 1. Chemical structures of pynp, bpy, and phen. 2+ ChartChart 2.2. [Ru(pynp)(NˆN)(CO)[Ru(pynp)(N^N)(CO)22]]2+ complexescomplexes in in this this study study [19]. [19]. Chart 2. [Ru(pynp)(N^N)(CO)2]2+ complexes in this study [19]. 2. Results and Discussion 2. Results and Discussion 2. Results and Discussion 2.1. Diastereoselective Synthesis and Characterization of Ruthenium Complexes with the Asymmetric 2.1.pynp Diastereoselective Ligand Synthesis and Characterization of Ruthenium Complexes with the Asymmetric pynp 2.1. Diastereoselective Synthesis and Characterization of Ruthenium Complexes with the Asymmetric pynp Ligand 2.1.1.Ligand Synthesis and Structure of Complexes 2.1.1. Synthesis and Structure of Complexes 2.1.1.Unlike Synthesis unsubstituted and Structure 2,2’-bipyridine of Complexes and 1,10-phenanthroline, the pynp ligand has no C2 symmetry axis (ChartUnlike1 ),unsubstituted so metal complexes 2,2'-bipyridine containing and pynp(s) 1,10 may-phenanthroline, have several diastereomers.the pynp ligand We has previously no C2 Unlike unsubstituted 2,2'-bipyridine and 1,10-phenanthroline, the pynp ligand has no C2 symmetryreported that axis for (Chart ruthenium 1), so metal carbonyl complexes complexes cont containingaining pynp(s) both may bpy have and pynp,several formation diastereomers. of the symmetry axis (Chart 1), so metal complexes containing pynp(s) may have several diastereomers. Wedesired previously isomers reported can be controlled that for byruthenium the order carb of introductiononyl complexes of the containi two ligandsng both [18 bpy,20]. and Using pynp, this We previously reported that for ruthenium carbonyl complexes containing both bpy and pynp, formationmethod, dicarbonylruthenium of the desired isomers complexes can be controlled containing by both the pynp order and of phenintroduction were successfully of the two prepared. ligands formation of the desired isomers can be controlled by the order of introduction of the two ligands As[18,20]. in the Using previous this method, study, the dicarbonylruthenium distal isomer is produced complexes preferentially containing when both phen pynp is introducedand phen were first [18,20]. Using this method, dicarbonylruthenium complexes containing both pynp and phen were (Figuresuccessfully1a). In prepared. the case ofAsNˆN in the= previousbpy, the productstudy, th obtainede distal isomer by this is method produced is almost preferentially all the d -form,when successfully prepared. As in the previous study, the distal isomer is produced preferentially when whereasphen is introduced in the phen first system (Figure a small 1a). In quantity the case ofof theN^N corresponding = bpy, the productp-form obtained (10–20%) by isthis also method formed. is phen is introduced first (Figure 1a). In the case of N^N = bpy, the product obtained by this method is Thisalmost may all bethe due d-form, to energy whereas diff inerences the phen between system the ad small- and quantityp-isomers.
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