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Search for "thioether ligand" in Full Text gives 3 result(s) in Beilstein Journal of Organic Chemistry.
Switchable molecular tweezers: design and applications
- Pablo Msellem,
- Maksym Dekthiarenko,
- Nihal Hadj Seyd and
- Guillaume Vives
Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45
- metalloporphyrin arms [83] or larger assemblies [78]. In particular, remarkable double tweezers (or triple-decker catalysts) 41 have been developed (Figure 22). These tweezers consist of two Rh(I) complexes, wherein a catalytically active metal Al(III)–salen arm is shared on the phosphine thioether ligand side
Graphical Abstract
Figure 1: Principle of switchable molecular tweezers.
Figure 2: Principle of pH-switchable molecular tweezers 1 [19].
Figure 3: a) pH-Switchable tweezers 2 substituted with alkyl chains as switchable lipids. b) Schematic depict...
Figure 4: Modification of spectral properties of 3 by controlled induction of Pt–Pt interactions.
Figure 5: Conformational switching of di(hydroxyphenyl)pyrimidine-based tweezer 4 upon alkylation or fluoride...
Figure 6: Hydrazone-based pH-responsive tweezers 5 for mesogenic modulation.
Figure 7: pH-Switchable molecular tweezers 6 bearing acridinium moieties.
Figure 8: a) Terpyridine and pyridine-hydrazone-pyridine analogs molecular tweezers and b) extended pyridine ...
Figure 9: Terpyridine-based molecular tweezers with M–salphen arms and their field of application. Figure 9 was adapt...
Figure 10: a) Terpyridine-based molecular tweezers for diphosphate recognition [48]; b) bishelicene chiroptical te...
Figure 11: Terpyridine-based molecular tweezers with allosteric cooperative binding.
Figure 12: Terpyridine-based molecular tweezers presenting closed by default conformation.
Figure 13: Pyridine-pyrimidine-pyridine-based molecular tweezers.
Figure 14: Coordination-responsive molecular tweezers based on nitrogen-containing ligands.
Figure 15: Molecular tweezers exploiting the remote bipyridine or pyridine binding to trigger the conformation...
Figure 16: Bipyridine-based molecular tweezers exploiting the direct s-trans to s-cis-switching for a) anion b...
Figure 17: a) Podand-based molecular tweezers [66,67]. b) Application of tweezers 32 for the catalytic allosteric reg...
Figure 18: Anion-triggered molecular tweezers based on calix[4]pyrrole.
Figure 19: Anion-triggered molecular tweezers.
Figure 20: a) Principle of the weak link approach (WLA) developed by Mirkin and its application to b) symmetri...
Figure 21: Molecular tweezers as allosteric catalyst in asymmetric epoxide opening [80].
Figure 22: Allosteric regulation of catalytic activity in ring-opening polymerization with double tweezers 41.
Figure 23: a) Conformational switching of 42 by intramolecular –S–S– bridge formation. b) Shift of conformatio...
Figure 24: a) Redox-active glycoluril-TTF tweezers 44. b) Mechanism of stepwise oxidation of said tweezers wit...
Figure 25: Mechanism of formation of the mixed-valence dimers of tweezers 45.
Figure 26: Mechanism of carbohydrate liberation upon redox-mediated conformation switching of 46.
Figure 27: a) The encapsulation properties of 47 as well as the DCTNF release process from its host–guest comp...
Figure 28: Redox-active bipyridinium-based tweezers. a) With a ferrocenyl hinge 49, b) with a propyl hinge 50 ...
Figure 29: Redox-active calix[4]arene porphyrin molecular tweezers.
Figure 30: a) Mechanism of the three orthogonal stimuli. b) Cubic scheme showing the eight different states of ...
Figure 31: Redox-controlled molecular gripper based on a diquinone resorcin[4]arene.
Figure 32: a) Shinkai's butterfly tweezers and their different host–guest properties depending on the isomer. ...
Figure 33: Cyclam-tethered tweezers and their different host–guest complexes depending on their configuration.
Figure 34: Azobenzene-based catalytic tweezers.
Figure 35: Photoswitchable PIEZO channel mimic.
Figure 36: Stilbene-based porphyrin tweezers for fullerene recognition.
Figure 37: Stiff-stilbene-based tweezers with urea or thiourea functional units for a) anion binding, b) anion...
Figure 38: Feringa’s photoswitchable organocatalyst (a) and different catalyzed reactions with that system (b)....
Figure 39: a) Irie and Takeshita’s thioindigo-based molecular tweezers. b) Family of hemithioindigo-based mole...
Figure 40: Dithienylethylene crown ether-bearing molecular tweezers reported by Irie and co-workers.
Self-assembled coordination thioether silver(I) macrocyclic complexes for homogeneous catalysis
- Zhen Cao,
- Aline Lacoudre,
- Cybille Rossy and
- Brigitte Bibal
Beilstein J. Org. Chem. 2019, 15, 2465–2472, doi:10.3762/bjoc.15.239
- -atropisomer, as revealed by X-ray diffraction. This alkylaryl thioether ligand (L) formed different macrocyclic complexes by coordination with silver(I) salts depending on the nature of the anion: M2L2 for AgOTf and AgOTFA, M6L4 for AgNO3. A discrete M2L complex was obtained in the presence of bulky PPh3AgOTf
- ; homogeneous catalysis; prochiral; silver complex; thioether ligand; Introduction Since the early advances in the late eighties [1][2][3][4][5][6][7][8][9][10], silver(I) catalysis has been widely exploited based on the versatile redox and soft Lewis acid properties of this coinage metal cation. Silver
- (I) complexes can be discrete species [35][36][37][38], coordination driven supramolecules [35][42] or coordination polymers [39][40][42]. To the best of our knowledge, silver crown thioether complexes were never reported as catalysts. Recently, we described a flexible bis-dialkyl thioether ligand
Graphical Abstract
Scheme 1: Synthesis of ligand 1, as its syn-atropisomer.
Figure 1: X-ray structures of complex 1a, as two diastereoisomeric macrocycles (R,S-1)2·(AgOTf)2 with ligands...
Figure 2: X-ray structure of complex 1c, as a (R,S-1)4·(AgNO3)6 cage with three nitrate anions as coordinatin...
Figure 3: X-ray structure of complex 1d, as a racemic mixture of (R,R)- and (S,S)-(syn-1)·(PPh3AgOTf)2.
Figure 4: Variable temperature 1H NMR of complex 1a in CDCl3 (7 mM) from −30 °C to 60 °C.
True and masked three-coordinate T-shaped platinum(II) intermediates
- Manuel A. Ortuño,
- Salvador Conejero and
- Agustí Lledós
Beilstein J. Org. Chem. 2013, 9, 1352–1382, doi:10.3762/bjoc.9.153
Graphical Abstract
Figure 1: Qualitative orbital diagram for a d8 metal in ML4 square-planar and ML3 T-shaped complexes.
Figure 2: Walsh diagram for the d-block of a d8 ML3 complex upon bending of one L–M–L angle.
Figure 3: Neutral Y-shaped Pt complex Y1 [15]. Angles are given in degrees.
Figure 4: General classification of T-shaped Pt(II) structures according to the fourth coordination site.
Figure 5: Hydride, boryl and borylene true T-shaped Pt(II) complexes.
Figure 6: NHC-based true T-shaped Pt(II) complexes.
Figure 7: Phosphine-based agostic T-shaped Pt(II) complexes. Compounds in brackets correspond with hydrido–al...
Figure 8: Phenylpyridine and NHC-based agostic T-shaped Pt(II) complexes.
Figure 9: Counteranion coordination in T-shaped Pt(II) complexes.
Figure 10: Phosphine-based solvento Pt(II) complexes.
Figure 11: Nitrogen-based solvento Pt(II) complexes.
Figure 12: Pincer-based solvento Pt(II) complexes.
Figure 13: Structure of the QM/MM optimized cisplatin–protein adduct [94].
Figure 14: NMR coupling constants used for the characterization of three-coordinate Pt(II) species.
Figure 15: The chemical formula of the complexes discussed in Table 2.
Scheme 1: Halogen abstraction from 1.
Scheme 2: Halogen abstraction from 2 forming the dicationic complex T3 [22].
Scheme 3: Hydrogenation of complexes A5a and A5b [39].
Scheme 4: Hydrogenation of complexes 3 and A5c [40].
Scheme 5: Intermolecular C–H bond activation from T5a [28].
Scheme 6: Protonation of complexes 4 [35,36].
Scheme 7: Cyclometalation of 5 [43].
Scheme 8: Protonation of 6.
Scheme 9: Reductive elimination of ethane from 7.
Scheme 10: Reductive elimination of methane from six-coordinate Pt(IV) complexes.
Scheme 11: Proposed dissociative mechanism for the fluxional motion of dmphen in [Pt(Me)(dmphen)(PR3)]+ comple...
Figure 16: Feasible interactions for unsaturated intermediates 11b (left) and 12b (right) during fluxional mot...
Scheme 12: Halogen abstraction from 13a,b and subsequent cyclometalation to yield complexes A5a,b [39].
Scheme 13: Proposed mechanism for the acid-catalyzed cyclometalation of 14 via intermediate 15 [41].
Scheme 14: Proposed mechanism for the formation of 19 [102].
Scheme 15: Cyclometalation of 20 via thioether dissociation [117].
Figure 17: Gibbs energy profile (in chloroform solvent) for the cyclometalation of 23 [120].
Scheme 16: Coordination of tmtu to 29 and subsequent C–H bond activation via three-coordinate species 31 and 32...
Scheme 17: Cyclometalation process of NHC-based Pt(II) complexes [28,44].
Scheme 18: Cyclometalation process of complex A9 [43].
Scheme 19: “Rollover” reaction of 38 and subsequent oligomerization [123].
Scheme 20: Proposed mechanism for the formation of cyclometalated species 44 [124].
Scheme 21: Self-assembling process of 45 by “rollover” reaction [126].
Scheme 22: “Rollover” reaction of A9. Energies (solvent) in kcal mol−1 [127].
Scheme 23: Proposed mechanisms for the “rollover” cyclometalation of 52 in gas-phase ion-molecule reactions [128].
Scheme 24: β-H elimination and 1,2-insertion equilibrium involving A1d and the subsequent generation of 57 [35].
Scheme 25: Proposed mechanism for thermolysis of 7b and 7c in benzene-d6 and cyclohexane-d12 solvents [101].
Scheme 26: β-H elimination process of A11a [28].
Scheme 27: Intermolecular C–H bond activation from 62 [95].
Scheme 28: Reductive elimination of methane from 65 followed by CD3CN coordination or C–D bond-activation proc...
Figure 18: DFT-optimized structures describing the κ2 (69, left) and κ3 (69’, right) coordination modes of [Pt...
Scheme 29: Intermolecular arene C–H bond activation from NHC-based complexes [28].
Figure 19: Energy profiles (in benzene solvent) for the benzene C–H bond activation from A11a, A11b, T5a and T...
Scheme 30: Intermolecular arene C–H bond activation from PNP-based complex 71 [12].
Scheme 31: Intermolecular C–H bond-activation by gas-phase ion-molecule reactions of 74 [7,142].
Scheme 32: Dihydrogen activation through complexes A5a, A5b [39], A5c [40] and S1a [54].
Scheme 33: Dihydrogen activation through complexes A7 and 16 [41]. For a: see Scheme 13.
Scheme 34: Br2 and I2 bond activations through complexes A11a and T5a [143].
Scheme 35: Detection and isolation of the Pt(III) complex 81a [143].
Scheme 36: Cl2 bond activation through complexes 82 and 83 [144].
Scheme 37: cis–trans Isomerization mechanism of the solvento Pt(II) complexes S5 [2,61].
Figure 20: Energy profiles for the isomerization of complexes [Pt(R)(PMe3)2(NCMe)]+ where R means Me (85a, red...
Figure 21: DFT-optimized structure of intermediate 86 [62]. Bond distances in angstrom and angles in degrees.
Scheme 38: Proposed dissociative ligand-substitution mechanism of cis-[Pt(R)2S2] complexes (87) [117].
Scheme 39: Proposed mechanisms for the ligand substitution of the dinuclear species 91 [146].
