scholarly journals Selective oxo ligand functionalisation and substitution reactivity in an oxo/catecholate-bridged UIV/UIV Pacman complex

2020 ◽  
Vol 11 (27) ◽  
pp. 7144-7157 ◽  
Author(s):  
Bradley E. Cowie ◽  
Iskander Douair ◽  
Laurent Maron ◽  
Jason B. Love ◽  
Polly L. Arnold
Keyword(s):  
Oxo Ligand

A UIV/UIV “Pacman” complex exhibits facile oxo-ligand functionalisation and substitution reactivity, owing to a bridging catecholate ligand that enhances the μ-oxo nucleophilicity and stabilises the resulting products.

Dramatic Increase in the Rate of Olefin Insertion by Coordination of Lewis Acids to the Oxo Ligand in Oxorhenium(V) Hydrides

2017 ◽  
Vol 36 (10) ◽  
pp. 2042-2051 ◽  
Author(s):  
Nikola S. Lambic ◽  
Caleb A. Brown ◽  
Roger D. Sommer ◽  
Elon A. Ison
Keyword(s):  
Lewis Acids ◽  
Oxo Ligand

Preparation and Structure of Tetraphenylarsonium Bis[1,2-Dicyanoethenedithiolato]oxotechnetate(V)

1988 ◽  
Vol 41 (1) ◽  
pp. 151 ◽  
Author(s):  
SF Colmanet ◽  
MF Mackay
Keyword(s):  
Bond Distance ◽  
Apical Position ◽  
Space Group ◽  
Ethanol Yields ◽  
Oxo Ligand

The reaction of sodium 1,2-dicyanoethenedithiolate with [AsPh4][TcOCl4] in ethanol yields crystals of [AsPh4][ TcO ( mnt )2] (1). Crystals of (1) are monoclinic and belong to the space group P21/c with a 12.636(1), b 13.749(1), c 18.484(1)Ǻ, β 93.49(1)� with Z 4. Refinement on 3669 data measured with Cu Kα radiation converged at R 0.063. The structure consists of [ TcO ( mnt )2]- anions and [AsPh4]+ cations. The technetium(V) atom is five-coordinate with the four sulfur atoms in the basal positions and the oxo ligand in the apical position, to give a distorted square-pyramidal environment about the technetium. The Tc =O bond distance is 1.655(6)Ǻ.

An unusual ditantalum (Ta:Ta) compound with a bridging oxo ligand

1983 ◽  
Vol 22 (6) ◽  
pp. 868-870 ◽  
Author(s):  
F. Albert Cotton ◽  
Wieslaw J. Roth
Keyword(s):  
Oxo Ligand

Zur Umsetzung von ReO2I(PPh3)2 mit PhNCO. Synthese und Kristallstrukturen von ReO2I(PPh3)2 · CHCl3, [ORe(OCONPh)I(PPh3)]3, Re(NPh)(NH2Ph)I2(PPh3)(OCONHPh) und Re(NPh)(NH2Ph)I2(PPh3) ( OReO3) / On the Reaction of ReO2I(PPh3)2 with PhNCO. Synthesis and Crystal Structures of ReO2I(PPh3)2 · CHCl3, [ORe(OCONPh)I(PPh3)]3, Re(NPh)(NH2Ph)I2(PPh3)(OCONHPh) and Re(NPh)(NH2Ph)I2(PPh3) ( OReO3)

1991 ◽  
Vol 46 (2) ◽  
pp. 235-244 ◽  
Author(s):  
S. Schmid ◽  
J. Strähle
Keyword(s):  
Hydrolysis Product ◽  
Phosphine Ligands ◽  
Partial Hydrolysis ◽  
Monoclinic Space Group ◽  
Linear Arrangement ◽  
Triclinic Space Group ◽  
Metal Centers ◽  
Space Group ◽  
Trimeric Complex ◽  
Oxo Ligand

PhNCO reacts with oxo ligands at metal centers to form phenyl nitrene complexes. As an intermediate of this reaction we obtained with ReO2I(PPh3)2 (1) the trimeric complex [ORe(OCONPh)I(PPh3)]3 (2) in which the PhNCO moiety was added to an oxo ligand to form an N -phenyl carbamato group. This group acts as a bridging ligand chelating one Re atom via its N and one O atom and coordinating an other Re atom by its second O atom . 2 crystallizes as 2 · 2 CHCl3 in the triclinic space group P1̄ with a = 1423.1(5), b = 2443.3(7), c = 1403.8(6) pm , α = 92.31(3), β = 94.76(3), γ = 81.48(3)°, and Z = 2. From the mother liquor of 2 after a few days Re(NPh)(NH2Ph)I2(PPh3)(OCONHPh) (3) is formed as a partial hydrolysis product. 3 is monoclinic with the space group P21/n and a = 1163.0(4), b = 2527.0(3), c = 1243.9(5) pm, β = 98.04°, Z = 4. The Re atom exhibits an octahedral coordination w ith the two I atom s in a ?ra«s-arrangem ent and the phenyl nitrene ligand trans to the m onodentate PhN HCO2 group. The coordination is completed by a phosphine and an aniline ligand. Reaction of 2 with excess PPh3 yields 1. It crystallizes from CHCl3 as 1 · CHCl3 in the monoclinic space group P21/n with a = 975.9(3), b = 2731(1), c = 1417.3(6) pm , β = 93.35° and Z = 4. In 1 the Re atom is pentacoordinated in form of a trigonal bipyram id with the two phosphine ligands in axial positions. A solution of 2 in THF forms Re(NPh)(NH2Ph)I2(PPh3) (OReO3) (4) upon exposure to air at room temperature. 4 is obtained as orthorhombic crystals with the space group Pca21 and a = 1727(1), b = 1064.2(4), c = 1765.7(9) pm , Z = 4, and is an analogue of 3 from which it can be derived by substituting the carbamato ligand by a perrhenat ion. In 3 and 4 the phenyl nitrene ligand is bound by a Re = N triple bond of 172 pm in a linear arrangement Re = N - Ph .

Properties and reactivities of nonheme iron(iv)–oxo versus iron(v)–oxo: long-range electron transfer versus hydrogen atom abstraction

2014 ◽  
Vol 16 (41) ◽  
pp. 22611-22622 ◽  
Author(s):  
Baharan Karamzadeh ◽  
Devendra Singh ◽  
Wonwoo Nam ◽  
Devesh Kumar ◽  
Sam P. de Visser
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Long Range ◽  
Cation Radical ◽  
Nonheme Iron ◽  
Hydrogen Atom Abstraction ◽  
Computational Studies ◽  
Radical Species ◽  
Oxo Ligand

Computational studies show that the perceived nonheme iron(v)–oxo is actually an iron(iv)–oxo ligand cation radical species.

Facets of Induced Internal Redox Involving WS42 - and WSe42 - : Synthesis and X-Ray Crystal Structures of syn-W2S2(μ-S)2(S2PPh2)2 and WO(Se2)(S2CNEt2)2

2000 ◽  
Vol 53 (9) ◽  
pp. 779 ◽  
Author(s):  
Edward R. T. Tiekink ◽  
Aston A. Eagle ◽  
Charles G. Young
Keyword(s):  
Crystal Structures ◽  
Redox Process ◽  
Space Group ◽  
X Ray ◽  
Complex Features ◽  
Oxo Ligand

Reaction of (NEt4)2[WS4] and [S2PPh2]2 in acetonitrile results in the formation of diamagnetic, orange syn-W2S2(µ-S) 2(S2PPh2)2 by an induced internal redox process. Crystals of the toluene solvate W2S2(µ-S) 2(S2PPh2)2 . C7H8 are triclinic and belong to space group P1– with a 13.845(5), b 16.536(7), c 8.387(2) Å, α 99.75(3), β 95.51(3), γ 83.08(3)˚, and Z 2. Refinement of 5445 data converged at R 0.038 and Rw 0.038. The complex possesses a syn-[W V 2S2(µ-S)2]2+ core with a W–W bond of 2.8161(5) Å and two terminal W=S bonds of 2.097(3) and 2.096(3) Å. The W-(µ-S) bond distances are in the range 2.310(2)–2.315(2) Å. Each of the five-coordinate, square-pyramidal tungsten atoms is further coordinated by a bidentate dithiophosphinate ligand with W–S bond distances ranging from 2.464(2) to 2.481(2) Å. Extended reaction of (NH4)2[WSe4] and [S2CNEt2]2 in acetonitrile produces green WS(Se2)(S2CNEt2)2 and red WO(Se2)(S2CNEt2)2 in 40% and 15% yields, respectively. Crystals of WO(Se2)(S2CNEt2)2 are monoclinic and belong to space group P21/n with a 9.609(6), b 15.053(7), c 13.120(9) Å, β 100.08(4)˚, and Z 4. Refinement of 2473 data converged at R 0.039 and Rw 0.039. The seven-coordinate, pentagonal bipyramidal complex features C1 symmetry, an axial oxo ligand (W=O 1.705(6) Å), an equatorial, side-on bonded diselenido ligand (W–Se(1) 2.509(1), W–Se(2) 2.547(1) Å, Se(1)–Se(2) 2.306(2) Å) and two bidentate dithiocarbamate ligands.

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