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Ligand redox non-innocent behaviour in ruthenium complexes of ethynyl tolans

A small series of half-sandwich bis(phosphine) ruthenium acetylide complexes [Ru(C?CC6H4C?CSiMe 3)(L2)Cp?] and [Ru(C?CC6H 4C?CC6H4R-4)(L2)Cp?] (R = OMe, Me, CO2Me, NO2; L2 = (PPh 3)2, Cp? = Cp; L2 = dppe; Cp? = Cp?) have been synthesised. One-electron oxidations of these complexes gave the corresponding radical cations, which were significantly more chemically stable in the case of the Ru(dppe)Cp? derivatives. The representative complex [Ru(C?CC6H4C?CC 6H4OMe-4)(dppe)Cp?] was further examined by spectroelectrochemical (IR and UV-Vis-NIR) methods. The results of the spectroelectrochemical studies, supported by DFT calculations, indicate that the hole is largely supported by the ‘RuC?CC6H4’ moiety in a manner similar to that described previously for simple aryl ethynyl complexes, rather than being more extensively delocalized along the entire conjugated ligand.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Small bite-angle diphosphines – Synthesis and structure of low-valent complexes of bis(di-orthotolylphosphino)methane (dotpm) and related ligands

The coordination chemistry of bis(di-ortho-tolylphosphino)methane (dotpm) has been studied. It is an excellent chelating ligand and a range of low-valent mononuclear complexes have been prepared; cis-[M(CO)4(eta 2-dotpm)] (M = Cr, Mo, W; 1-3), [CpRuCl(eta2-dotpm)] (4), and cis-[MX2(eta2-dotpm)] (M = Pt, X = Cl, Br, I; 5a-5c, M = Pd, X = Cl; 6). The backbone protons are relatively acidic and can be deprotonated using n-BuLi or LiN(SiMe3)2. Subsequent alkylation by RX (X = halogen; R = Me, Et, CH2Ph) affords cis-[M(CO)4(eta2-Rdotpm)] (M = Cr, Mo, W, R = Me; 7-9, M = Mo, W, R = Et, CH2Ph; 12-15), [CpRuCl(eta2-Medotpm)] (10), and cis-[PtI2(eta2-Medotpm)] (11). Thermolysis of cis-[Mo(CO)4(eta2-Medotpm)] (8) yields what is believed to be the coordinately and electronically unsaturated complex [Mo(CO) 3(eta2-Medotpm)] (16), suggesting that derivatives of dotpm (cone angle 194) are bulky enough to stabilize a 16-electron complex. Crystal structures of 2, 3, 7-9, 13, and 14 have been determined (diphosphine bite angles ranging from 66.58(3) to 70.96(5).

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Ruthenium-catalyzed two-component addition to form 1,3-dienes: Optimization, scope, applications, and mechanism

A two component coupling of an allene and an activated olefin to form 1,3-dienes has been developed. The requisite allenes are synthesized either from terminal alkynes by a one carbon homologation using copper(I) iodide, paraformaldehyde, and diisopropylamine, via an ortho ester-Claisen rearrangement from a propargylic alcohol, or via a Wittig type reaction on a ketene generated in situ from an acid chloride. Mono- through tetrasubstituted allenes could be synthesized by these methods. Either cyclopentadienylruthenium(II) cyclooctadiene chloride or cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate catalyze the addition reaction. When the former catalyst is employed, an alkyne activator is added to help generate the active catalyst. Through systematic optimization studies, a range of conditions was examined. The optimal conditions consisted of the use of cerium(III) trichloride heptahydrate as a cocatalyst in dimethylformamide as a solvent at 60 C. The reaction was found to be chemoselective, and a wide range of functionality was tolerated, including esters, alcohols, nitriles, and amides. When substituted allenes are used, good selectivity can be obtained with proper substitution. A mechanism involving a ruthenacycle is proposed to account for the selectivity or lack thereof in product formation. With disubstituted allenes, selectivity is obtained when beta-hydrogen elimination is favored from a specific site. In tri- and tetrasubstituted allenes, steric issues concerning the C-C bond forming event appear to be the dominant factor in determining product formation. This process represents a highly atomeconomical synthesis of 1,3-dienes in a controlled fashion. The utility of the 1,3-diene products was demonstrated by their use in Diels-Alder reactions to form a variety of cyclic systems including polycyclic structures. This sequence represents a convergent atom economic method for ring formation by a series of simple additions.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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The synthesis, structure, and electrochemical properties of Fe(C?CC?N)(dppe)Cp and related compounds

The cyanoacetylide complex Fe(C?CC?N)(dppe)Cp (3) is readily obtained from sequential reaction of Fe(C?CSiMe3)(dppe)Cp with methyllithium and phenyl cyanate. Complex 3 is a good metalloligand, and coordination to the metal fragments [RhCl(CO)2], [Ru(PPh 3)2Cp]+, and [Ru(dppe)Cp*]+ affords the corresponding cyanoaceylide-bridged heterobimetallic complexes. In the case of the 36-electron complexes [Cp(dppe)Fe-C?CC?N-ML n]n+, spectroscopic and structural data are consistent with a degree of charge transfer from the iron centre to the rhodium or ruthenium centre via the C3N bridge, giving rise to a polarized ground state. Electrochemical and spectroelectrochemical methods reveal significant interactions between the metal centres in the oxidized (35 electron) derivatives, [Cp(dppe)Fe-C?CC?N-MLn](n+1)+.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Synthesis of dinuclear and trinuclear ruthenium cyclopropenyl complexes

The preparation of dinuclear ruthenium cyclopropenyl complexes by the deprotonation of vinylidene complexes was presented. Diastereomeric pairs of 1:1 ratio were obtained. The deprotonation reaction of a couple of the products led to the formation of dinuclear bis-furyl complexes. Other complexes obtained are also reported. The complexes were characterized by X-ray diffraction analysis and spectroscopic methods.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Discovery and Comparison of Homogeneous Catalysts in a Standardized HOT-CAT Screen with Microwave-Heating and qNMR Analysis: Exploring Catalytic Hydration of Alkynes

A HOT-CAT (homogeneous thermal catalysis) screen using microwave-heating and quantitative NMR (qNMR) analysis has been developed for identification and comparison of catalyst activity in homogeneous metal-based catalysis. The hydration of terminal alkynes to ketones or aldehydes served as a model reaction in this proof-of-concept study. Key aspects of the screen are the use of a high-temperature setting (e. g., 160 C) at a fixed, short reaction time (e. g., 15 min) for all samples. Analysis of crude reaction mixtures by a standardized, quantitative 1H NMR protocol gives a comprehensive picture of catalyst chemo- and regioselectivity, which permits broad comparisons and the discovery of non-target reactivity. For catalytic alkyne hydration, data for 105 runs involving 81 catalyst systems with 15 different metals is presented. The activity of all established catalyst systems was reproduced, and new catalyst systems with Markovnikov hydration selectivity were discovered and applied to preparative runs, namely Cu2O?CSA (CSA=camphorsulfonic acid), Co(OAc)2?tetraphenylporphyrin?CSA and [IrCl(COD)]?CSA.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Some Transition Metal Complexes of Pentakis(methoxycarbonyl)cyclopentadiene: Water-soluble Metallocenes, and the X-Ray Crystal Structure of Ru(eta-C5H5)

Some metal derivatives of the – anion (cpp-) are described, of which transition metal complexes M(cpp)2 are fully ionised in aqueous solution and the mixed complex Ru(eta-C5H5) contains a symmetrically bonded cpp ring; covalent Group IB metal complexes MI(cpp)(PPh3) react further with PPh3 to give ionic (cpp).

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Study of half sandwich platinum group metal complexes containing tetradentate N-donor ligand bearing two di-pyridylamine units linked by an aromatic spacer

A general approach for the preparation of dinuclear eta5- and eta6-cyclic hydrocarbon platinum group metal complexes, viz. [(eta6-arene)2Ru2(NN?NN)Cl 2]2+ (arene = C6H6, 1; p- iPrC6H4Me, 2; C6Me6, 3), [(eta5-C5Me5)2M 2(NN?NN)Cl2]2+ (M = Rh, 4; Ir, 5), [(eta5-C5H5)2M2(NN? NN)(PPh3)2]2+ (M = Ru, 6; Os, 7), [(eta5-C5Me5)2Ru 2(NN?NN)(PPh3)2]2+ (8) and [(eta5-C9H7)2Ru 2(NN?NN)(PPh3)2]2+ (9), bearing the bis-bidentate ligand 1,2-bis(di-2-pyridylaminomethyl)benzene (NN?NN), which contains two chelating di-pyridylamine units connected by an aromatic spacer, is reported. The cationic dinuclear complexes have been isolated as their hexafluorophosphate or hexafluoroantimonate salts and characterized by use of a combination of NMR, IR and UV-vis spectroscopic methods and by mass spectrometry. The solid state structure of three derivatives, [2][SbF 6]2, [3][PF6]2 and [4][PF 6]2, has been determined by X-ray structure analysis.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Coordinating Tectons. Experimental and Computational Infrared Data as Tools to Identify Conformational Isomers and Explore Electronic Structures of 4-Ethynyl-2,2?-bipyridine Complexes

4-Ethynyl-2,2?-bipyridyl-substituted ruthenium alkynyl complexes have been prepared and used to access a range of binuclear homometallic ruthenium and heterometallic ruthenium-rhenium complexes. These have been characterized by a variety of spectroscopic and single-crystal X-ray diffraction experiments. The IR spectra of a number of these ruthenium alkynyls display multiple nu(C?C) bands in the IR spectra, which are rationalized in terms of putative conformational isomers, whose calculated infrared stretching frequencies are comparable to those obtained experimentally. The mononuclear alkynyl ruthenium complexes undergo reversible one-electron oxidations centered largely on the alkynyl ligands, as inferred from the significant shift in nu(C?C) frequency on oxidation, while the binuclear complex [Ru{C?C-4-bpy-kappa2-N,N?-RuClCp}(dppe)Cp?]+ undergoes initial oxidation at the very electron rich {RuCl(bpy)Cp} fragment, causing only a small change in nu(C?C). A combination of IR and UV-vis spectroelectrochemical experiments, supported by quantum chemical calculations on a selected range of conformers, led to the classification of [Ru{C?C-4-bpy-kappa2-N,N?-RuClCp}(dppe)Cp?]+ as a weakly coupled class II mixed-valence compound (Hab = 306 cm-1). These results indicate that there is improved electronic communication through the 4-ethynyl-2,2?-bipyridyl ligand in comparison to the analogous 5-ethynyl-2,2?-bipyridyl complexes (Hab = 17 cm-1).

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Preparation and characterization of novel poly(alkylidenamine) nitrile ruthenium metallodendrimers

Complete functionalization of N,N,N?,N?-[tetrakis(cyanoethyl)- hexamethylenediamine] [N=C(CH2)2]2N(CH 2)6N[(CH2)2-C=N]2 (4) and N,N,N’,N’-[tetrakis(cyanoethoxypropyl)hexamethylenediamine] [N=C(CH 2)2O(CH2)3]2N(CH 2)6N[(CH2)3-O(CH2) 2C=N]2 (7) with the organometallic moiety [Ru(eta5-C5H5)(PPh3) 2Cl] and the five-coordinate cis-[RuCl(dppe)2]-[PF 6] [dppe = 1,2-bis(diphenylphosphanyl)ethane] was attained, with good yield, respectively, by treating the metallofragment with the core in methanol (at room temperature and in presence of T1PF6 as a chloride abstractor) and in 1,2-dichloroethane (under reflux). These novel nitrile-functionalized poly(alkylidenamine) dendrimers peripherally functionalized with the ruthenium moieties [Ru(eta5-C 5H5)(PPh3)2]+ and [RuCl(dppe)2]+ (8-11) were fully characterized by NMR (1H, 13C, 31P), TOF-MS and FTIR. The present results represent a step forward in the knowledge of the most adequate synthetic strategy for total coordination of poly(alkylidenamine) nitrile core derivatives to the different ruthenium complex moieties and confirm the versatility of these systems as building blocks in metallodendrimer chemistry.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI