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Synthesis of uranium(VI) terminal oxo complexes: molecular geometry driven by the inverse trans-influence (2012)

Kosog, Boris ; La Pierre, Henry S ; Heinemann, Frank W ; [et al.]

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Language: English

In: Journal of the American Chemical Society, 21 March 2012, Vol.134(11), pp.5284-9

Description: Oxidation of our previously reported uranium(V) oxo complexes, supported by the chelating ((R)ArO)(3)tacn(3-) ligand system (R = tert-butyl (t-Bu), 1-t-Bu; R = 1-adamantyl (Ad), 1-Ad), yields terminal uranium(VI) oxo complexes [(((R)ArO)(3)tacn)U(VI)(O)]SbF(6) (R = t-Bu, 2-t-Bu; R = Ad, 2-Ad). These complexes differ in their molecular geometry in that 2-t-Bu possesses pseudo-C(s) symmetry in solution and solid state as the terminal oxo ligand lies in the equatorial plane (as defined by the three aryloxide arms of the ligand) in order to accommodate the thermodynamic preference of high-valent uranium oxo complexes to have a σ- and π-donating ligand trans to the oxo (vis-à-vis the ubiquity of the linear UO(2)(2+) moiety). The distortion of the ligand--which stands in contrast to all other complexes of uranium supported by the ((R)ArO)(3)tacn(3-) ligand, including 2-Ad--is most clearly seen in the structures of 2-t-Bu, [(((t-Bu)ArO)(3)tacn)U(VI)(O)(eq)]SbF(6), and 3-t-Bu, [(((t-Bu)ArO)(3)tacn)U(VI)(O)(eq)(OC(O)CF(3))(ax)]. The solid-state structure of 3-t-Bu reveals that the trans U-O(ArO) bond length is shortened by 0.1 Å in comparison to the cis U-O(ArO) bonds and the trans U-O-C(ipso) angle is linearized (157.67° versus 147.85° and 130.03°). Remarkably, the minor modification of the ligand to have Ad groups at the ortho positions of the aryloxide arms is sufficient to stabilize a C(3v)-symmetric terminal uranium(VI) oxo complex (2-Ad) without a ligand trans to the oxo. These experimental results were reproduced in DFT calculations and allow the qualitative bracketing of the relative thermodynamic stabilization afforded by the inverse trans-influence as ∼6 kcal mol(-1).

Keywords: Chemical Bonds -- Analysis ; Density Functional Theory -- Usage ; Oxidation-reduction Reactions -- Analysis ; Oxo Compounds -- Chemical Properties ; Oxo Compounds -- Structure ; Uranium Compounds -- Chemical Properties ; Uranium Compounds -- Structure;

ISSN: 00027863

E-ISSN: 1520-5126

DOI: 10.1021/ja211618v

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2

Article

Pushing Electrons—Which Carbene Ligand for Which Application? (2018)

Meyer, Karsten

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Language: English

In: Organometallics, 02/12/2018, Vol.37(3), pp.273-274

ISSN: 0276-7333

E-ISSN: 1520-6041

DOI: 10.1021/acs.organomet.7b00720

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3

Article

Uranium(III)-mediated C-C-coupling of terminal alkynes: formation of dinuclear uranium(IV) vinyl complexes (2012)

Kosog, Boris ; Kefalidis, Christos E ; Heinemann, Frank W ; [et al.]

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Language: English

In: Journal of the American Chemical Society, 01 August 2012, Vol.134(30), pp.12792-7

Description: The previously reported uranium(III) complex [(((Ad)ArO)(3)N)U(III)(DME)] (1; Ad = adamantane, DME = 1,2-dimethoxyethane) reacts with the terminal bis-alkynes 1,7-octadiyne or 1,6-heptadiyne in C-C-coupling reactions to form the uranium(IV) vinyl complexes [{(((Ad)ArO)(3)N)U(IV)}(2)(μ-η(2):η(1)-1,2-(CH)(2)-cyclohexane)] (2) and [{(((Ad)ArO)(3)N)U(IV)}(2)(μ-η(2):η(2)-1,2-(CH)(2)-cyclopentane)] (3). With the monoalkynes 1-hexyne or 4-(t)butyl-phenylacetylene, the complexes [{(((Ad)ArO)(3)N)U(IV)}(2)(μ-η(2)(C1):η(1)(C4)-2-(n)Bu-1,3-octadiene)] (4) and [{(((Ad)ArO)(3)N)U(IV)}(2)(μ-η(2)(C4):η(1)(C1)-1,3-di-(p-(t)Bu-phenyl)butadiene))] (5), are formed. These are the first four examples of uranium vinyl complexes that are reported and crystallographically characterized. In addition, detailed DFT calculations are presented to establish a possible mechanism for their formation and explain the differences found for the coordination of the hydrocarbon fragments. In contrast to a previously proposed monometallic pathway for catalytic hydroamination of alkynes and alkyne dimerization involving a uranium vinyl intermediate at uranium(III) complexes, the calculations clearly support a bimetallic mechanism, since its transition states are energetically the most favored.

Keywords: Alkynes -- Chemical Properties ; Catalysis -- Analysis ; Chemical Bonds -- Analysis ; Density Functional Theory -- Usage ; Uranium Compounds -- Chemical Properties ; Vinyl Compounds -- Chemical Properties;

ISSN: 00027863

E-ISSN: 1520-5126

DOI: 10.1021/ja3047393

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4

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Spin crossover in a four-coordinate iron(II) complex (2011)

Scepaniak, Jeremiah J ; Harris, T David ; Vogel, Carola S ; [et al.]

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Language: English

In: Journal of the American Chemical Society, 23 March 2011, Vol.133(11), pp.3824-7

Description: The four-coordinate iron(II) phosphoraniminato complex PhB(MesIm)(3)Fe-N═PPh(3) undergoes an S = 0 to S = 2 spin transition with T(C) = 81 K, as determined by variable-temperature magnetic measurements and Mössbauer spectroscopy. Variable-temperature single-crystal X-ray diffraction revealed that the S = 0 to S = 2 transition is associated with an increase in the Fe-C and Fe-N bond distances and a decrease in the N-P bond distance. These structural changes have been interpreted in terms of electronic structure theory.

Keywords: Chemistry;

ISSN: 00027863

E-ISSN: 1520-5126

DOI: 10.1021/ja2003473

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5

Article

Brigitte Gedek Science Award 2012 for Mycotoxin Research (2012)

Meyer, Karsten

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Language: English

In: Mycotoxin Research, Feb, 2012, Vol.28(1), p.77(1)

Description: Byline: Karsten Meyer (1) Author Affiliation: (1) Lehrstuhl fur Tierhygiene, Technische Universitat Munchen, Weihenstephaner Berg 3, 85354, Freising, Germany Article History: Registration Date: 23/11/2011 Online Date: 15/12/2011

Keywords: Anatomy & Physiology;

ISSN: 0178-7888

E-ISSN: 18671632

DOI: 10.1007/s12550-011-0120-9

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Synthesis, structure, and reactivity of an iron(V) nitride (2011)

Scepaniak, Jeremiah J ; Vogel, Carola S ; Khusniyarov, Marat M ; [et al.]

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Language: English

In: Science (New York, N.Y.), 25 February 2011, Vol.331(6020), pp.1049-52

Description: Despite being implicated as important intermediates, iron(V) compounds have proven very challenging to isolate and characterize. Here, we report the preparation of the iron(V) nitrido complex, [PhB((t)BuIm)(3)Fe(V)≡N]BAr(F24) (PhB((t)BuIm)(3)(-) = phenyltris(3-tert-butylimidazol-2-ylidene)borato, BAr(F24) = B(3,5-(CF(3))(2)C(6)H(3))(4)(-)), by one electron oxidation of the iron(IV) nitrido precursor. Single-crystal x-ray diffraction of the iron(V) complex reveals a four-coordinate metal ion with a terminal nitrido ligand. Mößbauer and electron paramagnetic resonance spectroscopic characterization, supported by electronic structure calculations, provide evidence for a d(3) iron(V) metal center in a low spin (S = 1/2) electron configuration. Low-temperature reaction of the iron(V) nitrido complex with water under reducing conditions leads to high yields of ammonia with concomitant formation of an iron(II) species.

Keywords: Ferric Compounds -- Chemistry ; Iron -- Chemistry

ISSN: 00368075

E-ISSN: 1095-9203

DOI: 10.1126/science.1198315

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7

Article

Manganese nitride complexes in oxidation states III, IV, and V: synthesis and electronic structure (2012)

Kropp, Henning ; King, Amanda E ; Khusniyarov, Marat M ; [et al.]

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Language: English

In: Journal of the American Chemical Society, 19 September 2012, Vol.134(37), pp.15538-44

Description: The synthesis and characterization of a series of manganese nitrides in a tripodal chelating tris(carbene) ligand framework is described. Photolysis of [(TIMEN(xyl))Mn(N(3))](+) (where TIMEN(xyl) = tris[2-(3-xylylimidazol-2-ylidene)ethyl]amine) yields the isolable molecular Mn(IV) nitride, [(TIMEN(xyl))Mn(N)](+). Spectroscopic and DFT studies indicate that this Mn(IV) d(3) complex has a doublet electronic ground state. The metal-centered one-electron oxidation of this Mn(IV) species results in formation of the pentavalent Mn(V) nitride, [(TIMEN(xyl))Mn(N)](2+). Unlike previously reported, tetragonal Mn(V) nitrides with a d(2), nonmagnetic S = 0 ground state, this trigonal bipyramidal complex has a triplet ground state S = 1. One-electron reduction of [(TIMEN(xyl))Mn(N)](+) produces the neutral, nonmagnetic trivalent [(TIMEN(xyl))Mn(N)] species with a d(4) low-spin, S = 0, ground state.

Keywords: Manganese -- Chemistry

ISSN: 00027863

E-ISSN: 1520-5126

DOI: 10.1021/ja306647c

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8

Article

Redox control of a ring-opening polymerization catalyst (2011)

Broderick, Erin M ; Guo, Neng ; Vogel, Carola S ; [et al.]

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Language: English

In: Journal of the American Chemical Society, 22 June 2011, Vol.133(24), pp.9278-81

Description: The activity of an yttrium alkoxide complex supported by a ferrocene-based ligand was controlled using redox reagents during the ring-opening polymerization of L-lactide. The oxidized complex was characterized by X-ray crystallography and (1)H NMR, XANES, and Mössbauer spectroscopy. Switching in situ between the oxidized and reduced yttrium complexes resulted in a change in the rate of polymerization of L-lactide. Synthesized polymers were analyzed by gel permeation chromatography. Polymerization of trimethylene carbonate was also performed with the reduced and oxidized forms of an indium alkoxide complex. The indium system showed the opposite behavior to that of yttrium, revealing a metal-based dependency on the rate of polymerization.

Keywords: Mossbauer Spectroscopy -- Usage ; Oxidation-reduction Reactions -- Analysis ; Ring-opening Polymerization -- Analysis ; X-ray Crystallography -- Usage ; Yttrium Compounds -- Chemical Properties ; Yttrium Compounds -- Structure;

ISSN: 00027863

E-ISSN: 1520-5126

DOI: 10.1021/ja2036089

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9

Article

One-pot synthesis of an Fe(II) bis-terpyridine complex with allosterically regulated electronic properties (2012)

Machan, Charles W ; Adelhardt, Mario ; Sarjeant, Amy A ; [et al.]

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Language: English

In: Journal of the American Chemical Society, 17 October 2012, Vol.134(41), pp.16921-4

Description: Herein we report the one-pot synthesis of Fe(II) bis-terpyridine complexes with two peripheral square-planar Pt(II) bis-phosphinoalkylthioether moieties. These novel structures, which exhibit allosterically controllable electronic properties, are made by taking advantage of two orthogonal and high-yielding reactions. The prototypical complex can be structurally regulated through the reversible abstraction and introduction of chloride ions to the Pt(II) centers. This moves the Fe(II) center and two Pt(II) metal centers into and out of communication with each other, causing changes in the electronic structure of the complex and its corresponding optical and redox properties. The start and end points of the allosterically regulated system have been characterized by single-crystal X-ray diffraction and NMR, UV-vis, and (57)Fe Mößbauer spectroscopy.

Keywords: Electrons ; Ferrous Compounds -- Chemical Synthesis ; Pyridines -- Chemistry

ISSN: 00027863

E-ISSN: 1520-5126

DOI: 10.1021/ja3045019

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10

Article

A mononuclear Fe(III) single molecule magnet with a 3/2↔5/2 spin crossover (2012)

Mossin, Susanne ; Tran, Ba L ; Adhikari, Debashis ; [et al.]

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Language: English

In: Journal of the American Chemical Society, 22 August 2012, Vol.134(33), pp.13651-61

Description: The air stable complex [(PNP)FeCl(2)] (1) (PNP = N[2-P(CHMe(2))(2)-4-methylphenyl](2)(-)), prepared from one-electron oxidation of [(PNP)FeCl] with ClCPh(3), displays an unexpected S = 3/2 to S = 5/2 transition above 80 K as inferred by the dc SQUID magnetic susceptibility measurement. The ac SQUID magnetization data, at zero field and between frequencies 10 and 1042 Hz, clearly reveal complex 1 to have frequency dependence on the out-of-phase signal and thus being a single molecular magnet with a thermally activated barrier of U(eff) = 32-36 cm(-1) (47-52 K). Variable-temperature Mössbauer data also corroborate a significant temperature dependence in δ and ΔE(Q) values for 1, which is in agreement with the system undergoing a change in spin state. Likewise, variable-temperature X-band EPR spectra of 1 reveals the S = 3/2 to be likely the ground state with the S = 5/2 being close in energy. Multiedge XAS absorption spectra suggest the electronic structure of 1 to be highly covalent with an effective iron oxidation state that is more reduced than the typical ferric complexes due to the significant interaction of the phosphine groups in PNP and Cl ligands with iron. A variable-temperature single crystal X-ray diffraction study of 1 collected between 30 and 300 K also reveals elongation of the Fe-P bond lengths and increment in the Cl-Fe-Cl angle as the S = 5/2 state is populated. Theoretical studies show overall similar orbital pictures except for the d(z(2)) orbital, which has the most sensitivity to change in the geometry and bonding, where the quartet ((4)B) and the sextet ((6)A) states are close in energy.

Keywords: Chemistry;

ISSN: 00027863

E-ISSN: 1520-5126

DOI: 10.1021/ja302660k

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