Syntheses and characterization of five-coordinate copper(II) complexes based on tridentate SNS pincer ligand precursors

Miecznikowski, John R.; Lynn, Matthew A.; Jasinski, Jerry P.; Lo, Wayne; Bak, Daniel W.; Pati, Mekhala; Butrick, Elizabeth E.; Drozdoski, Anne Elise R.; Archer, Kerry A.; Villa, Christine E.; Lemons, Elise G.; Powers, Erin; Siu, Margaret; Gomes, Camile D.; Bernier, Nicholas A.; Morio, Kaitlyn N.

doi:10.1016/j.poly.2014.03.020

Cited by 17 publications

(6 citation statements)

References 44 publications

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“…The structure shown in Fig. 45 This twisted rac-geometry (atropisomerism) is also in contrast with CCC-NHC complexes, which exhibit planar conformations of the 5,5-fused metallacycles. The conformation of 3 contrasts with a previously reported SNS complex, which exhibited the meso-conformation due to the preferred tetrahedral geometry of the d 10 Zn metal center.…”

Section: Crystallographymentioning

confidence: 94%

“…43 While it is similar to the racconformation of the S-N-S ligand reported in 5-coordinate Cu complexes. 45 This twisted rac-geometry (atropisomerism) is also in contrast with CCC-NHC complexes, which exhibit planar conformations of the 5,5-fused metallacycles. [52][53][54] Furthermore, the rac-conformation of 3 has a chiral twist similar to the 5,6-fused-ring systems reported by Odinets 29 and to the 5,5-fused-ring complexes synthesized by Kruithof and coworkers.…”

Section: Crystallographymentioning

confidence: 99%

“…[17][18][19]34,35 Additionally, thione and bisthione ligands have been successfully applied in catalysis. [38][39][40] In this regard, the only metal complexes containing pincer-type ligands containing NHTs are the copper(I), copper(II), and zinc (II) compounds reported by Miecznikowski and coworkers [41][42][43][44][45] and the rhodium(I) and iridium(I) derivatives synthesized by Jia, Huang and Jin. [38][39][40] In this regard, the only metal complexes containing pincer-type ligands containing NHTs are the copper(I), copper(II), and zinc (II) compounds reported by Miecznikowski and coworkers [41][42][43][44][45] and the rhodium(I) and iridium(I) derivatives synthesized by Jia, Huang and Jin.…”

Section: Introductionmentioning

confidence: 99%

“…36,37 It is noteworthy that pincer complexes incorporating N-heterocyclic thione (NHT) donor groups are virtually unknown even though the coordination chemistry of simple monodentate NHTs has been extensively investigated. [38][39][40] In this regard, the only metal complexes containing pincer-type ligands containing NHTs are the copper(I), copper(II), and zinc (II) compounds reported by Miecznikowski and coworkers [41][42][43][44][45] and the rhodium(I) and iridium(I) derivatives synthesized by Jia, Huang and Jin. 46 Herein, we report the synthesis of a 1,3 phenylene-bridged bis(NHT) ligand precursor and its successful metalation, producing the first SCS pincer complex incorporating NHT groups.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, characterization, photophysical properties, and catalytic activity of an SCS bis(N-heterocyclic thione) (SCS-NHT) Pd pincer complex

et al. 2015

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Treatment of 1,3-bis(3'-butylimidazolyl-1'-yl)benzene diiodide with elemental sulfur in the presence of a base produced a bis(N-heterocyclic thione) (NHT) pincer ligand precursor. Its reaction with PdCl2(CH3CN)2 produced chloro[1,3-bis(3'-butylimidazole-2'-thione-κ-S)benzene-κ-C]palladium(ii), a 6,6-fused ring SCS-NHT palladium pincer complex. This air stable compound is, to our knowledge, the first SCS pincer complex that utilizes N-heterocyclic thione (NHT) donor groups. The molecular structures of the ligand precursor and the palladium complex were determined by X-ray crystallography and computational studies provided insight into the interconversion between its rac and meso conformations. The photophysical properties of the complex were established, and its catalytic activity in Suzuki, Heck, and Sonogashira cross-coupling reactions was evaluated.

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Section: Crystallographymentioning

confidence: 94%

Section: Crystallographymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis, characterization, photophysical properties, and catalytic activity of an SCS bis(N-heterocyclic thione) (SCS-NHT) Pd pincer complex

et al. 2015

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“…Due to their ideal disposition of electron donor atoms, pincer ligands can form complexes with various transition metals. Both pincer compounds and the resulting metal complexes have a range of interesting properties including catalytic potential, 4 electrochemical features, [5][6][7][8] biochemical applications, [9][10][11][12][13] interaction between organic molecules and metal surfaces [14][15][16] and polymerization 1 that all have been investigated previously.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Fe and Cu metal complexes derived from ‘SNS’ Pincer type ligands and their efficient catalyst precursors for the chemical fixation of $$\hbox {CO}_{2}$$ CO 2

et al. 2019

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Two novel tridentate SNS pincer type ligands, 2,6-bis[[(2-methoxyphenyl)thio]methyl]pyridine (L1) and 2,6-bis[[(2-chlorophenyl)thio]methyl]pyridine (L2), each possessing two sulfur and one nitrogen donor functionalities (SNS), based on 2,6-bis(thioether)pyridine ligands were prepared and metallised with CuCl 2 • 2H 2 O and FeCl 2 • 4H 2 O metal salts. Two new unanticipated complexes were obtained from the L2 ligand, the dimeric bidentate Cu(I) complex [Cu 2 (κ 2 −L2) 2 Cl 2 ] and tridentate Fe(II) complex [Fe(κ 3 −L2)Cl 2 ] while two new tridentate pincer-type complexes M(κ 3-L1)Cl 2 ] (M = Cu, Fe) were formed from the L1 ligand. It was observed that the structure of this Cu(I) complex has a tetrahedral geometry using single crystal Xray diffraction analysis. In addition, catalytic properties of metal complexes towards the formation of cyclic carbonates from CO 2 and epoxides were investigated. The less sterically hindered Fe(II) complex with the L1 ligand [Fe(κ 3 −L1)Cl 2 ] (2) showed the best catalytic activity. Several parameters including temperature, time, epoxide identity and CO 2 pressure were investigated to find the optimum catalytic reaction conditions. Moreover, DFT studies of these compounds are presented in the study.

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Homoleptic Mononuclear Tris‐Chelate Complexes of Fe^II, Co^II, Ni^II, and Zn^II Based on a Redox‐Active Imidazolyl‐2‐thione Ligand: Structural and Electrochemical Correlation

et al. 2020

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Five mononuclear tris‐chelate complexes of FeII, CoII, NiII and ZnII, containing the bidentate ligand 3‐methyl‐1‐(2‐pyridyl)imidazolyl‐2‐thione (L), have been synthesised and characterised, namely [MII(L)3](BF4)2, where M = Fe (1), Co (2), Ni (3) and Zn (4), and [FeII(L)3](PF6)2 {1‐(PF6)2}. The complexes have been characterised by standard methods and single‐crystal X‐ray diffraction, showing that all the complexes are isostructural and isomorphs, crystallising in the P1 space group, except for 1‐(PF6)2, which crystallises in the P21/c, as expected due to the different size and symmetry of the anion. The metal centre is found in a distorted meridional‐N3S3 octahedral geometry. In all the complexes, two ligand strands within the same complex cation unit interact via an almost perfect face‐to‐face π–π stacking. The double intramolecular interaction occurs between a pyridyl ring of one ligand strand and an imidazolyl ring of a second ligand strand and vice versa. The FeII and CoII complexes, 1 and 2, are stabilised in the high spin state, based on the bond lengths and angles obtained by SC‐XRD and by VT‐magnetic studies in the solid state and NMR Evans method in CD3CN solution. The cyclic voltammetry behaviour for compounds 1–4 showed an EC mechanism for the oxidation process, in which two ligand strands are electrochemically oxidised, instead of the metal centre, followed by a chemical process (de‐coordination and dimerisation). Whereas, the reduction process involved metal electrodeposition for the FeII, NiII and ZnII complexes. In the case of the CoII complex, the voltammetric response suggested a multistep decomposition process during the electrochemical reduction. Finally, a linear correlation between the oxidation potential of the ligand and the average M–N bond length has been found, permitting the modification of the oxidation potential by selection of the metal centre.

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Syntheses and characterization of five-coordinate copper(II) complexes based on tridentate SNS pincer ligand precursors

Cited by 17 publications

References 44 publications

Synthesis, characterization, photophysical properties, and catalytic activity of an SCS bis(N-heterocyclic thione) (SCS-NHT) Pd pincer complex

Synthesis, characterization, photophysical properties, and catalytic activity of an SCS bis(N-heterocyclic thione) (SCS-NHT) Pd pincer complex

Synthesis of Fe and Cu metal complexes derived from ‘SNS’ Pincer type ligands and their efficient catalyst precursors for the chemical fixation of $$\hbox {CO}_{2}$$ CO 2

Homoleptic Mononuclear Tris‐Chelate Complexes of Fe^II, Co^II, Ni^II, and Zn^II Based on a Redox‐Active Imidazolyl‐2‐thione Ligand: Structural and Electrochemical Correlation

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Syntheses and characterization of five-coordinate copper(II) complexes based on tridentate SNS pincer ligand precursors

Cited by 17 publications

References 44 publications

Synthesis, characterization, photophysical properties, and catalytic activity of an SCS bis(N-heterocyclic thione) (SCS-NHT) Pd pincer complex

Synthesis, characterization, photophysical properties, and catalytic activity of an SCS bis(N-heterocyclic thione) (SCS-NHT) Pd pincer complex

Synthesis of Fe and Cu metal complexes derived from ‘SNS’ Pincer type ligands and their efficient catalyst precursors for the chemical fixation of $$\hbox {CO}_{2}$$ CO 2

Homoleptic Mononuclear Tris‐Chelate Complexes of FeII, CoII, NiII, and ZnII Based on a Redox‐Active Imidazolyl‐2‐thione Ligand: Structural and Electrochemical Correlation

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Homoleptic Mononuclear Tris‐Chelate Complexes of Fe^II, Co^II, Ni^II, and Zn^II Based on a Redox‐Active Imidazolyl‐2‐thione Ligand: Structural and Electrochemical Correlation