model complexes
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Author(s):  
Hyeonglim Seo ◽  
Kathleen E. Prosser ◽  
Mark Kalaj ◽  
Johannes Karges ◽  
Benjamin L. Dick ◽  
...  

2021 ◽  
Vol 11 (8) ◽  
pp. 3327
Author(s):  
Danilo Vona ◽  
Roberta Ragni ◽  
Emiliano Altamura ◽  
Paola Albanese ◽  
Maria Michela Giangregorio ◽  
...  

In vivo incorporation of a series of organometallic photoluminescent complexes in Phaeodactylum tricornutum diatom shells (frustules) is investigated as a biotechnological route to luminescent biosilica nanostructures. [Ir(ppy)2bpy]+[PF6]−, [(2,2′-bipyridine)bis(2-phenylpyridinato)iridium(III) hexafluorophosphate], [Ru(bpy)3]2+ 2[PF6]−, [tris(2,2′-bipyridine)ruthenium(II) hexafluorophosphate], AlQ3 (tris-(8-hydroxyquinoline)aluminum), and ZnQ2 (bis-8-hydroxyquinoline-zinc) are used as model complexes to explore the potentiality and generality of the investigated process. The luminescent complexes are added to the diatom culture, and the resulting luminescent silica nanostructures are isolated by an acid-oxidative treatment that removes the organic cell matter without altering both frustule morphology and photoluminescence of incorporated emitters. Results show that, except for ZnQ2, the protocol successfully leads to the incorporation of complexes into the biosilica. The spontaneous self-adhering ability of both bare and doped Phaeodactylum tricornutum cells on conductive indium tin oxide (ITO)-coated glass slides is observed, which can be exploited to generate dielectric biofilms of living microorganisms with luminescent silica shells. In general, this protocol can be envisaged as a profitable route to new functional nanostructured materials for photonics, sensing, or biomedicine via in vivo chemical modification of diatom frustules with organometallic emitters.


2021 ◽  
Author(s):  
Tanner Jankins ◽  
William Bell ◽  
Yu Zhang ◽  
Zi-Yang Qin ◽  
Milan Gembicky ◽  
...  

Tungsten catalysis has played an instrumental role in the history of organometallic chemistry, with electrophilic, fully oxidized W(VI) catalysts featuring prominently in olefin polymerization and metathesis reactions. Here, we report that the simple W(0) precatalyst, W(CO)<sub>6</sub>, catalyzes the isomerization and hydrocarbonylation of alkenes via a W(0)/W(II) redox couple. The 6- to 7-coordinate geometry changes associated with this redox process are key in allowing isomerization to take place over multiple positions and stop at a defined unactivated internal site that is primed for <i>in situ</i> functionalization. DFT studies and crystallographic characterization of multiple directing-group-bound W(II) model complexes illuminate potential intermediates of this redox cycle and showcase the capabilities of the 7-coordinate W(II) geometry to facilitate challenging alkene functionalizations.


2021 ◽  
Author(s):  
Tanner Jankins ◽  
William Bell ◽  
Yu Zhang ◽  
Zi-Yang Qin ◽  
Milan Gembicky ◽  
...  

Tungsten catalysis has played an instrumental role in the history of organometallic chemistry, with electrophilic, fully oxidized W(VI) catalysts featuring prominently in olefin polymerization and metathesis reactions. Here, we report that the simple W(0) precatalyst, W(CO)<sub>6</sub>, catalyzes the isomerization and hydrocarbonylation of alkenes via a W(0)/W(II) redox couple. The 6- to 7-coordinate geometry changes associated with this redox process are key in allowing isomerization to take place over multiple positions and stop at a defined unactivated internal site that is primed for <i>in situ</i> functionalization. DFT studies and crystallographic characterization of multiple directing-group-bound W(II) model complexes illuminate potential intermediates of this redox cycle and showcase the capabilities of the 7-coordinate W(II) geometry to facilitate challenging alkene functionalizations.


Author(s):  
Serena DeBeer ◽  
Rebeca G. Castillo ◽  
Anselm W. Hahn ◽  
Benjamin E. Van Kuiken ◽  
Justin T. Henthorn

2021 ◽  
Author(s):  
Serena DeBeer ◽  
Rebeca G. Castillo ◽  
Anselm W. Hahn ◽  
Benjamin E. Van Kuiken ◽  
Justin T. Henthorn

2021 ◽  
Author(s):  
Fanjun Zhang ◽  
Toby John Woods ◽  
Lingyang Zhu ◽  
Thomas Rauchfuss

The mechanism for inhibition of [FeFe]-hydrogenases by formaldehyde is examined with model complexes.  Key findings: (i) CH2 donated by formaldehyde covalently link Fe and the amine cofactor, blocking the active site and...


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