Shuttling of Nickel OxidationStates in N4S2 Coordination Geometry versusDonor Strength of TridentateN2S Donor Ligands

Shuttling of Nickel Oxidation
States in N4S2 Coordination Geometry versus
Donor Strength of Tridentate
N2S Donor Ligands:

Inorganic Chemistry

DOI: 10.1021/ic300606g

Platinum(0) Complexes with Alkynylphosphane Ligands

Platinum(0) Complexes with Alkynylphosphane Ligands:

Abstract

The reactivity of the Pt⁰ derivative [Pt₂(dba)₃] (dba = trans,trans-dibenzylideneacetone) towards PPh₂C≡CR [R = Ph, tolyl (Tol), C₅H₄N-2] and PPh₂C≡CPPh₂ (dppa) has been explored. Treatment of [Pt₂(dba)₃] with PPh₂C≡CR (8 equiv.) in THF gave the tetrahedral complexes [Pt(PPh₂C≡CR)₄] [R = Ph (1), Tol (3), C₅H₄N-2 (5)], whereas reactions with a molar ratio of 1:4 afforded the binuclear derivatives [{Pt(PPh₂C≡CR)(μ-κP:η²-PPh₂C≡CR)}₂] [R = Ph (2), Tol (4) X-ray, C₅H₄N-2 (6)], which were shown to be generated through the mononuclear complexes 1, 3 and 5 as intermediate species. An analogous reaction using 4 equiv. of PPh₂C≡CPPh₂ afforded [Pt₂(PPh₂C≡CPPh₂)₂(μ-κ²PP′-PPh₂C≡CPPh₂)₃] (7), in which two “Pt(PPh₂C≡CPPh₂)” fragments are joined through three bridging dppa ligands (μ-κ²PP′-PPh₂C≡CPPh₂). Attempts to crystallize 7 at –30 °C afforded crystals of [Pt₂{PPh₂C≡CP(O)Ph₂}₂(μ-κ²PP′-PPh₂C≡CPPh₂)₃] (8) by oxidation of the free end of the terminal dppa ligands. The compound was characterized by X-ray diffraction.

Tetrahedral Pt⁰ complexes [Pt(PPh₂C≡CR)₄], which evolve into binuclear derivatives [{Pt(PPh₂C≡CR)(μ-κP:η²-PPh₂C≡CR)}₂] [R = Ph, tolyl, C₅H₄N-2], and binuclear compounds stabilized by a (μ-PPh₂C≡CPPh₂)₃ triply bridging system have been prepared and fully characterized.

Hydride-Bridged NiRh Complexeswith Tunable N3S2 Dithiolato Ligands and TheirUtilization asCatalysts for Hydrogenation of Aldehydes and CO2 in AqueousMedia

Hydride-Bridged NiRh Complexes
with Tunable N3S2 Dithiolato Ligands and Their
Utilization as
Catalysts for Hydrogenation of Aldehydes and CO2 in Aqueous
Media:

Organometallics

DOI: 10.1021/om300350u

Role of a Noninnocent Pincer Ligand in the Activation of CO2 at (PNN)Ru(H)(CO)

Role of a Noninnocent
Pincer Ligand in the Activation
of CO2 at (PNN)Ru(H)(CO):

Organometallics

DOI: 10.1021/om300403b

Structural investigations into the deactivation pathway of the CO2 reduction electrocatalyst Re(bpy)(CO)3Cl

Structural investigations into the deactivation pathway of the CO2 reduction electrocatalyst Re(bpy)(CO)3Cl:

Chem. Commun., 2012, Advance Article
DOI: 10.1039/C2CC32617E, Communication

Eric E. Benson, Clifford P. Kubiak
We report a series of complexes synthesized from the chemical reduction of the fac-tricarbonyl complex Re(bpy)(CO)₃Cl relevant to the electrocatalytic reduction of carbon dioxide.
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Cobalt-dithiolene complexes for proton reduction. [Chemistry]

Cobalt-dithiolene complexes for proton reduction. [Chemistry]: Artificial photosynthesis (AP) is a promising method of converting solar energy into fuel (H2). Harnessing solar energy to generate H2 from H+ is a crucial process in systems for artificial photosynthesis. Widespread application of a device for AP would rely on the use of platinum-free catalysts due to the scarcity of noble metals. Here we report a series of cobalt dithiolene complexes that are exceptionally active for the catalytic reduction of protons in aqueous solvent mixtures. All catalysts perform visible-light-driven reduction of protons from water when paired with as the photosensitizer and ascorbic acid as the sacrificial donor. Photocatalysts with electron withdrawing groups exhibit the highest activity with turnovers up to 9,000 with respect to catalyst. The same complexes are also active electrocatalysts in 1∶1 acetonitrile/water. The electrocatalytic mechanism is proposed to be ECEC, where the Co dithiolene catalysts undergo rapid protonation once they are reduced to . Subsequent reduction and reaction with H+ lead to H2 formation. Cobalt dithiolene complexes thus represent a new group of active catalysts for the reduction of protons.

Phosphane-Pyridine Iron Complexes: Synthesis, Characterization and Application in Reductive Amination through the Hydrosilylation Reaction

Phosphane-Pyridine Iron Complexes: Synthesis, Characterization and Application in Reductive Amination through the Hydrosilylation Reaction:

Abstract

A series of 6 cyclopentadienyl phosphanyl-pyridine piano-stool iron complexes was prepared in good yields, characterized, and studied in the catalytic reductive amination of benzaldehyde derivatives through hydrosilylation reactions by using polymethylhydrosiloxane as the hydrosilane source and in dimethylcarbonate as the solvent at 40 °C. Single-crystal X-ray structural analyses were performed for all the complexes.

A series of 6 cyclopentadienyl phosphanyl-pyridine piano-stool iron complexes was prepared, characterized, and studied in the catalytic reductive amination of benzaldehyde derivatives in dimethylcarbonate through hydrosilylation reactions by using polymethylhydrosiloxane as the hydrosilane source.

A Copper (II)-ethylenediamine modified polyoxoniobate with photocatalytic H2 evolution activity under visible light irradiation

A Copper (II)-ethylenediamine modified polyoxoniobate with photocatalytic H2 evolution activity under visible light irradiation:

Dalton Trans., 2012, Accepted Manuscript
DOI: 10.1039/C2DT30663H, Communication

Zhen-Li Wang, Hua-Qiao Tan, Wei-Lin Chen, Yang-Guang Li, Enbo Wang
A new dimer polyoxoniobate K2[Cu(en)2]15[Nb24O72H8]2-39H2O (1) has been synthesized and systematically characterized. Visible light photocatalytic H2 evolution activity was researched with 1 as the visible-light photosensitizer and catalyst, cobaloximes [CoIII(dmgH)2pyCl]...
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Role of a NoninnocentPincer Ligand in the Activationof CO2 at (PNN)Ru(H)(CO)

Role of a Noninnocent
Pincer Ligand in the Activation
of CO2 at (PNN)Ru(H)(CO):

Organometallics

DOI: 10.1021/om300403b

A Molecular Light-DrivenWater Oxidation Catalyst

A Molecular Light-Driven
Water Oxidation Catalyst:

Journal of the American Chemical Society

DOI: 10.1021/ja300797g

Photocatalytic H2 production in aqueous solution with host-guest inclusions formed by insertion of an FeFe-hydrogenase mimic and organic dye into cyclodextrins respectively

Photocatalytic H2 production in aqueous solution with host-guest inclusions formed by insertion of an FeFe-hydrogenase mimic and organic dye into cyclodextrins respectively:

Energy Environ. Sci., 2012, Accepted Manuscript
DOI: 10.1039/C2EE22109H, Communication

Xueqiang Li, Mei Wang, Dehua Zheng, Kan Han, Jingfeng Dong, Licheng Sun
Bioinspired noble-metal-free supramolecular systems were constructed by host-guest inclusions of FeFe-hydrogenase mimic and organic dye into cyclodextrins, which give typically ninefold increase in TON, sixteenfold enhancement in quantum efficiency, and...
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Synthesis of Bis(N-heterocyclic carbene) Complexes of Iron(II) and Their Application in Hydrosilylation and Transfer Hydrogenation

Synthesis of Bis(N-heterocyclic
carbene) Complexes
of Iron(II) and Their Application in Hydrosilylation and Transfer
Hydrogenation:

Organometallics

DOI: 10.1021/om300298q

New Types of CO-Releasing Molecules (CO-RMs), Based on Iron Dithiocarbamate Complexes and [Fe(CO)3I(S2COEt)]

New Types of CO-Releasing
Molecules (CO-RMs), Based
on Iron Dithiocarbamate Complexes and [Fe(CO)3I(S2COEt)]:

Organometallics

DOI: 10.1021/om3003637

A Photo Lewis Acid Generator (PhLAG): Controlled Photorelease of B(C6F5)3

A Photo Lewis Acid Generator
(PhLAG): Controlled Photorelease
of B(C6F5)3:

Journal of the American Chemical Society

DOI: 10.1021/ja3042977

Photocatalytic Hydrogen Evolution from FeMoS-Based Biomimetic Chalcogels

Photocatalytic Hydrogen
Evolution from FeMoS-Based
Biomimetic Chalcogels:

Journal of the American Chemical Society

DOI: 10.1021/ja303640s

Iron(I) in Negishi Cross-Coupling Reactions

Iron(I) in Negishi Cross-Coupling
Reactions:

Journal of the American Chemical Society

DOI: 10.1021/ja303250t

Time Resolved Infrared Spectroscopy: Kinetic Studies of Weakly Binding Ligands in an Iron–Iron Hydrogenase Model Compound

Time Resolved Infrared
Spectroscopy: Kinetic Studies
of Weakly Binding Ligands in an Iron–Iron Hydrogenase Model
Compound:

Inorganic Chemistry

DOI: 10.1021/ic300785z

Oxygen Reduction Reactions of Monometallic Rhodium Hydride Complexes

Oxygen Reduction Reactions
of Monometallic Rhodium Hydride Complexes:

Inorganic Chemistry

DOI: 10.1021/ic300279z

Heteropolytopic Arsanylarylthiolato Ligands: Cis–Trans Isomerism of Nickel(II), Palladium(II), and Platinum(II) Complexes of 1-AsPh2-2-SHC6H4

Heteropolytopic Arsanylarylthiolato
Ligands: Cis–Trans
Isomerism of Nickel(II), Palladium(II), and Platinum(II) Complexes
of 1-AsPh2-2-SHC6H4:

Inorganic Chemistry

DOI: 10.1021/ic300002p

Combined Experimental–Theoretical Characterization of the Hydrido-Cobaloxime [HCo(dmgH)2(PnBu3)]

Combined Experimental–Theoretical
Characterization
of the Hydrido-Cobaloxime [HCo(dmgH)2(PnBu3)]:

Inorganic Chemistry

DOI: 10.1021/ic2024204

Reactions of the Tetrafluoroborate Complex [Mo2Cp2(κ2-F2BF2)(μ-PPh2)2(CO)]BF4 with Mono- and Bidentate Ligands Having E–H bonds (E = O, S, Se, N, P)

Reactions of the Tetrafluoroborate
Complex [Mo2Cp2(κ2-F2BF2)(μ-PPh2)2(CO)]BF4 with Mono-
and Bidentate Ligands Having E–H bonds (E = O, S, Se, N, P):

Inorganic Chemistry

DOI: 10.1021/ic300626y