Anionic Nickel(II) Complexeswith Doubly DeprotonatedPNP Pincer-Type Ligands and Their Reactivity toward CO2

Anionic Nickel(II) Complexes
with Doubly Deprotonated
PNP Pincer-Type Ligands and Their Reactivity toward CO2:

Organometallics

DOI: 10.1021/om3010838

Influence of the diamine on the reactivity of thiosulfonato ruthenium complexes with hydrosulfide (HS-)

Dalton Trans., 2013, Advance Article
DOI: 10.1039/C2DT31758C, Paper

Erwan Galardon, Hombeline Daguet, Patrick Deschamps, Pascal Roussel, Alain Tomas, Isabelle Artaud
The reaction of thiosulfonato ruthenium complexes [(p-cymene)Ru(bipy)(SSO₂Ar)]⁺ with the hydrosulfide anion SH^- is governed by the nature of the diamine.

Asymmetric Hydrogenation Using Rhodium Complexes Generated from Mixtures of Monodentate Neutral and Anionic Phosphorus Ligands

A series of monodentate neutral and anionic phosphorus ligands was synthesized and evaluated in the asymmetric rhodium-catalyzed hydrogenation of functionalized olefins by using either catalysts containing identical ligands or catalysts generated from mixtures of two different ligands. We expected that the combination of an anionic ligand with a neutral ligand would favor the formation of hetero over homo bis-ligand complexes due to charge repulsion. NMR spectroscopic studies confirmed that charge effects can indeed shift the equilibrium toward the hetero bis-ligand complexes. In several cases, the combination of a neutral phosphane with an anionic phosphane, one chiral and the other achiral, furnished significantly higher enantioselectivities than analogous mixtures of two neutral ligands. The best results were obtained with a mixture of an anionic phosphoramidite and a neutral phosphoric acid diester. It is supposed that in this case a hydrogen bond between the two ligands additionally stabilizes the hetero ligand combination.

Charge effects and hydrogen bonding favor the formation of rhodium hetero bis-ligand complexes from mixtures of neutral and anionic monodentate phosphorus ligands. The combination of a neutral phosphoric acid diester as a hydrogen donor and an anionic phosphoramidite as a hydrogen acceptor gives very high enantioselectivities in Rh-catalyzed hydrogenation reactions, thus exceeding the enantiomeric excesses of the corresponding homo bis-ligand complexes (see scheme).

Contrasting ProtonationBehavior of Diphosphido vsDithiolato Diiron(I) Carbonyl Complexes

Organometallics

DOI: 10.1021/om300997s

Robust Photogeneration of H2 in Water Using Semiconductor Nanocrystals and a Nickel Catalyst

A photoreduction system combining nanoparticulate light absorbers with a soluble molecular catalyst proves stable for weeks.

Authors: Zhiji Han, Fen Qiu, Richard Eisenberg, Patrick L. Holland, Todd D. Krauss

Iridium and Rhodium Complexes with the Hemilabile Ligand [2-(1,3-Dioxolane-2-yl)phenyl]diphenylphosphane – Behaviour in Solution and Structural Characterization

[MCl(L₂)]₂ (M = Ir, L₂ = 1,5-cyclooctadiene; M = Rh, L₂ = norbornadiene) reacts with [2-(1,3-dioxolane-2-yl)phenyl]diphenylphosphane (1) to afford [MCl(L₂)(P~O)] (M = Ir, 2; M = Rh, 3), in which the ligand is P-monodentate. Complex 3 reacts with AgClO₄ to give [Rh(Nbd)(PO)]ClO₄ (4), in which the ligand is P,O-bidentate. Complex 2 is static at room temp., whereas 3 and 4 undergo intramolecular exchanges, which are fast at room temperature and slow at 223 K. The conformational changes in 4 are still fast at 223 K. Complexes 2–4 react with CO to afford trans-[MCl(CO)(P~O)₂] (M = Ir, 5; M = Rh, 6) or trans-[Rh(CO)₂(P~O)₂]ClO₄ (7). Cyclooctadiene complexes react with PPh₂(o-C₆H₄CHO) to afford [MClH(PPh₂(o-C₆H₄CO))(PO] (M = Ir, 8; M = Rh, 9), in which 1 is chelating. Complex 8 contains a single diastereomer, is static in the 303–213 K range and reacts with CO to form [IrClH(PPh₂(o-C₆H₄CO))(P~O)(CO)] (10). Complex 9 contains two diastereomers 9a/9b in a 95:5 ratio that undergo interconversion, which is slow at low temperature, and reacts with CO to undergo reductive elimination of aldehyde, cleavage of the Rh–O bond and scrambling of phosphanes. A mixture of trans-[RhCl(CO)(κ¹-PPh₂(o-C₆H₄CHO))(P~O)] (11), 6 and trans-[RhCl(CO)(κ¹-PPh₂(o-C₆H₄CHO))₂] is formed. Bubbling of nitrogen transforms 11 back into 9. Compound 2 reacts with hydrogen to give the fluxional [IrCl(H)₂(P~O)(PO)] (12) with trans P atoms and cis H atoms, which attains coalescence at 203 K. Complex 12 reacts with mono- or bidentate ligands to afford static [IrCl(H)₂(P~O)₂L] (L = CO, 13; py, 14; nPrNH₂, 15) or [Ir(H)₂(P~O)₂(en)]BPh₄ (16, en = ethylenediamine). Abstraction of halide from 12 affords [Ir(H)₂(PO)₂]BPh₄ (17), which is fluxional owing to interconversion between only two of the possible four diastereomers, for which ΔH^‡ = 54.7 ± 0.7 kJ mol^–1 and ΔS^‡ = 4.7 ± 0.2 J K^–1 mol^–1. The X-ray structures of 8, 15 and 16 are also reported.

[2-(1,3-Dioxolane-2-yl)phenyl]diphenylphosphane (1) coordinates to M^I preferably as a κ¹-P ligand. M^III may afford κ²-P,O coordination in dynamic diastereomers such as A or B. A contains a single diastereomer if M = Ir or two diastereomers in a 95:5 ratio if M = Rh. B contains a mixture of only two diastereomers.

Selective Redox Activationof H2 or O2 in a [NiRu] Complex by AromaticLigand Effects

Ogo

Organometallics

DOI: 10.1021/om300833m

Synthesis, Structure,and Reactivity of Iridium(III)Complexes Containing a 4,6-Dimethyl-1,3-benzenediphenylimine PincerLigand

Inorganic Chemistry

DOI: 10.1021/ic302589b

Novel diiminopyridine

Oxidation and Reductionof Bis(imino)pyridine Iron Dinitrogen Complexes: Evidence for Formationof a Chelate Trianion.

Inorganic Chemistry

DOI: 10.1021/ic301675t

Copper-, Palladium-,and Platinum-Containing Complexes of an Asymmetric Dinucleating Ligand

Inorganic Chemistry DOI: 10.1021/ic301914u

Iron Sulfide CatalyzedRedox/Condensation CascadeReaction between 2-Amino/Hydroxy Nitrobenzenes and ActivatedMethyl Groups: A Straightforward Atom Economical Approach to 2-Hetaryl-benzimidazolesand -benzoxazoles

Journal of the American Chemical Society DOI: 10.1021/ja311780a

Characterization of a Macrocyclic end-on Peroxido Copper Complex

 

Thirty years on: The dinuclear copper peroxido complex [(tet b)CuO₂Cu(tet b)]²⁺ has been structurally characterized (see picture: Cu yellow, O red, N pink; tet b=rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). This complex is quite persistent in solution at room temperature and is the first example of a structurally characterized copper dioxygen adduct complex with a macrocyclic ligand based on earlier studies by Valentine et al.

NMR in Organometallic Chemistry. By Paul S. Pregosin.

:

Wiley-VCH, Weinheim, 2012. 392 pp., softcover, € 59.00.—ISBN 978-3527330133

need this book, probably will be ebook via library - spread the word

Simplifying Iron–Phosphine Catalysts for Cross-Coupling Reactions

Any old iron? Iron catalysts based on the widely available diphosphine ligand bis(diphenylphosphino)ethane have not previously fared particularly well in iron-catalyzed cross-coupling processes. However, this turns out not to be due to any inherently poor performance associated with the ligand, but rather the need to form a bis-chelate complex, either before or during the formation of an active Fe^I species.

Biomimetic model for [FeFe]-hydrogenase: Asymmetrically disubstituted diiron complex with a redox-active 2,2'-bipyridyl ligand

Dalton Trans DOI: 10.1039/C2DT32457A, Paper

Souvik Roy, Thomas L Groy, Anne Katherine Jones
[FeFe]-hydrogenases feature a unique active site in which the primary catalytic unit is directly coordinated via a bridging cysteine thiolate to a secondary, redox active [4Fe4S] unit. The goal of...

Not very interesting but she does propose that bipy is non-innocent

Redox active aluminium(III) complexes convert CO2 into MgCO3 or CaCO3 in a synthetic cycle using Mg or Ca metal

Chem. Commun., 2013, Advance Article
DOI: 10.1039/C2CC37208H, Communication

Thomas W. Myers, Louise A. Berben
Using concomitant redox and acid-base reactivity, conversion of CO₂ into MgCO₃ or CaCO₃, via regenerable (IP^-)₂Al(OH), is presented (IP = [small alpha]-iminopyridine).

Bioinspired catalytic nitrile hydration by dithiolato, sulfinato/thiolato, and sulfenato/sulfinato ruthenium complexes

Bioinspired catalytic nitrile hydration by dithiolato, sulfinato/thiolato, and sulfenato/sulfinato ruthenium complexes:

Chem. Commun., 2013, Advance Article
DOI: 10.1039/C2CC35256G, Communication

Davinder Kumar, Cesar A. Masitas, Tho N. Nguyen, Craig A. Grapperhaus
Sulfur-oxidation of nitrile hydratase inspired Ru(II) catalysts enhances hydration activity and reduces product inhibition.
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Four-electron reduction of dioxygen catalysed by dinuclear cobalt complexes bridged by bis(terpyridyl)anthracene

Four-electron reduction of dioxygen catalysed by dinuclear cobalt complexes bridged by bis(terpyridyl)anthracene:

Chem. Commun., 2013, Advance Article
DOI: 10.1039/C2CC36528F, Communication

Tohru Wada, Hidetaka Maki, Tomoyuki Imamoto, Hirokazu Yuki, Yuji Miyazato
We have prepared dinuclear cobalt complexes 1 and 2 linked in a co-facial configuration by bis(terpyridyl)anthracene as catalysts for chemical and electrochemical four-electron reductions of dioxygen.
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A photoactive basket-like metal-organic tetragon worked as an enzymatic molecular flask for light driven H2 production

A photoactive basket-like metal-organic tetragon worked as an enzymatic molecular flask for light driven H2 production:

Chem. Commun., 2013, 49,627-629
DOI: 10.1039/C2CC37853A, Communication

Cheng He, Jian Wang, Liang Zhao, Tao Liu, Jing Zhang, Chunying Duan
A photoactive basket-like metal-organic tetragon containing a carbazole photosensitizer was developed to capture the [FeFe]-H₂ases for light driven H₂ production.
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A stable and strongly luminescent dinuclear Cu(I) helical complex prepared from 2-diphenylphosphino-6-methylpyridine

A stable and strongly luminescent dinuclear Cu(I) helical complex prepared from 2-diphenylphosphino-6-methylpyridine:

Chem. Commun., 2013, Advance Article
DOI: 10.1039/C2CC37873F, Communication

Juan-Jose Cid, John Mohanraj, Meera Mohankumar, Michel Holler, Gianluca Accorsi, Lydia Brelot, Iwona Nierengarten, Omar Moudam, Adrien Kaeser, Beatrice Delavaux-Nicot, Nicola Armaroli, Jean-Francois Nierengarten
[Cu₂([small mu ]-dpPyMe)₃(CH₃CN)](BF₄)₂ exhibits a strong blue-greenish emission in the solid state.
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A highly sensitive and selective turn-on fluorescent chemosensor for palladium based on a phosphine-rhodamine conjugate

Chem. Commun., 2013, Advance Article
DOI: 10.1039/C2CC37746B

Songtao Cai, Yan Lu, Song He, Fangfang Wei, Liancheng Zhao, Xianshun Zeng
A fluorescent chemosensor for palladium species based on a conjugate of phosphine and rhodamine B shows an excellent palladium selectivity with a detection limit down to the 10^-9 M range.

Molecular engineering of a cobalt-based electrocatalytic nanomaterial for H2 evolution under fully aqueous conditions

Molecular engineering of a cobalt-based electrocatalytic nanomaterial for H2 evolution under fully aqueous conditions:

Nature Chemistry 5, 48 (2013).
doi:10.1038/nchem.1481

Authors: Eugen S. Andreiadis, Pierre-André Jacques, Phong D. Tran, Adeline Leyris, Murielle Chavarot-Kerlidou, Bruno Jousselme, Muriel Matheron, Jacques Pécaut, Serge Palacin, Marc Fontecave & Vincent Artero
Efficient hydrogen-evolving catalysts comprising readily available elements are needed if hydrogen is to be adopted as a clean alternative to fossil fuels. Now, a diimine–dioxime cobalt complex has been covalently attached to a carbon nanotube electrode to yield an active and robust electrocatalyst for hydrogen generation (55,000 turnovers in seven hours) from aqueous solutions.

A Heterogeneous NickelCatalyst for the Hydrogenolysisof Aryl Ethers without Arene Hydrogenation

A Heterogeneous Nickel
Catalyst for the Hydrogenolysis
of Aryl Ethers without Arene Hydrogenation:

Journal of the American Chemical Society

DOI: 10.1021/ja3085912

Cyclopentadiene–Phosphine/Palladium-CatalyzedCleavage of C–N Bonds in Secondary Amines: Synthesis of Pyrroleand Indole Derivatives from Secondary Amines and Alkenyl or Aryl Dibromides

Cyclopentadiene–Phosphine/Palladium-Catalyzed
Cleavage of C–N Bonds in Secondary Amines: Synthesis of Pyrrole
and Indole Derivatives from Secondary Amines and Alkenyl or Aryl Dibromides:

Journal of the American Chemical Society

DOI: 10.1021/ja308950d

Ligand Effects on theOverpotential for Dioxygen Reduction by Tris(2-pyridylmethyl)amineDerivatives

Ligand Effects on the
Overpotential for Dioxygen Reduction by Tris(2-pyridylmethyl)amine
Derivatives:

Inorganic Chemistry

DOI: 10.1021/ic301656x

Alkyne Dichotomy: Splittingof Bis(dialkylamino)acetylenes,Dimethoxyacetylene, Bis(methylthio)acetylene, and Their Heavier CongenersTo Give Carbyne Ligands in Iron Carbonyl Derivatives

Alkyne Dichotomy: Splitting
of Bis(dialkylamino)acetylenes,
Dimethoxyacetylene, Bis(methylthio)acetylene, and Their Heavier Congeners
To Give Carbyne Ligands in Iron Carbonyl Derivatives:

Organometallics

DOI: 10.1021/om3008426

Well-Defined Iron Catalystfor Improved Hydrogenationof Carbon Dioxide and Bicarbonate

Well-Defined Iron Catalyst
for Improved Hydrogenation
of Carbon Dioxide and Bicarbonate:

Journal of the American Chemical Society

DOI: 10.1021/ja307924a

A Functional [NiFe]-HydrogenaseModel Compound ThatUndergoes Biologically Relevant Reversible Thiolate Protonation

A Functional [NiFe]-Hydrogenase
Model Compound That
Undergoes Biologically Relevant Reversible Thiolate Protonation:

Journal of the American Chemical Society

DOI: 10.1021/ja309563p

Cleavage of Carbon MonoxidePromoted by a DinuclearTantalum Tetrahydride Complex

Cleavage of Carbon Monoxide
Promoted by a Dinuclear
Tantalum Tetrahydride Complex:

Organometallics

DOI: 10.1021/om300759p