Dalton Transactions Blog

Gigantic multinuclear transition metal cluster complexes have unique properties and reactivities.

Metalladithiolenes, along with their cluster complexes, are excellent compounds for studying multinucleation and electronic communication in mixed-valent states.  Electronic communication in mixed-valent states is particularly important for single-molecule magnets, enzymes and for the creation of molecular devices.  Ryota Sakamoto, Satoru Tsukada and Hiroshi Nishihara detail synthetic strategies for the successful multinucleation of metalladithiolenes in this Hot Perspective. 

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Multinuclear metalladithiolenes: focusing on electronic communication in mixed-valent states
Ryota Sakamoto, Satoru Tsukada and Hiroshi Nishihara

Here are some of the authors’ other recent Dalton Transactions publications:

Synchronized motion and electron transfer of a redox-active rotor
Shoko Kume and Hiroshi Nishihara
Dalton Trans., 2011,40, 2299-2305
DOI: 10.1039/C0DT01084G

Conjugation of Au11 cluster with Cys-rich peptides containing the α-domain of metallothionein
Shinya Ariyasu, Akira Onoda, Ryota Sakamoto and Takeshi Yamamura
Dalton Trans., 2009, 3742-3747
DOI: 10.1039/B900570F

Development of a versatile synthesis method for trinuclear Co(III), Rh(III), and Ir(III) dithiolene complexes, and their crystal structures and multi-step redox properties
Yusuke Shibata, Baohua Zhu, Shoko Kume and Hiroshi Nishihara
Dalton Trans., 2009, 1939-1943
DOI: 10.1039/B815560G

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Unique cooperation has been observed between rhenium atoms and non-innocent N-confused porphyrin ligands in new oxorhenium(V) complexes.

The simplest porphyrin, porphine (left), and the N-confused porphyrin used to synthesize unique oxorhenium complexes.

Hiroyuki Furuta et al. have synthesised two new porphyrin oxorhenium(V) complexes which have been shown to be remarkably effective at oxygen atom transport. Through a catalytic process the oxygen atom from pyridine N-oxide can be transferred to PPh₃ in a 97% yield, notably higher than that of some other rhenium(V) complexes. The authors propose that the reason for their success is the existence of a Re-C bond, believing that this bond is important for efficient oxygen transport.

Atom transport is at the heart of successful catalysis, and as usual nature has already beaten us to it. Galactose oxidase for example converts a primary alcohol into an aldehyde by transporting a hydrogen atom from one part of the enzyme to another. But if the oxygen atom transfer seen in these synthetic N-confused porphyrin oxorhenium(V) complexes can be extended to other systems, exciting advancements in the field of catalysis could be on the horizon.

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To find out more about these exciting new complexes and the atom transport they facilitate, take a look at the full Dalton Transactions communication.

Cooperation between metal and ligand in oxygen atom transport by N-confused porphyrin oxorhenium(V) complexes
Takaaki Yamamoto, Motoki Toganoh and Hiroyuki Furuta

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By Katie Renouf, Web Writer

Read more about the polymerization mechanism for FREE for 4 weeks at:

Lewis pair polymerization by classical and frustrated Lewis pairs: acid, base and monomer scope and polymerization mechanism
Yuetao Zhang, Garret M. Miyake, Mallory G. John, Laura Falivene, Lucia Caporaso, Luigi Cavallo and Eugene Y.-X. Chen
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT30427A

This article will form part of a themed issue on Frustrated Lewis Pairs guest edited by Douglas W. Stephan.  Other papers in this issue include:

Exchange chemistry of ^tBu₃P(CO₂)B(C₆F₅)₂Cl
Rebecca C. Neu, Gabriel Ménard and Douglas W. Stephan

Fixation of carbon dioxide and related small molecules by a bifunctional frustrated pyrazolylborane Lewis pair
Eileen Theuergarten, Janin Schlösser, Danny Schlüns, Matthias Freytag, Constantin G. Daniliuc, Peter G. Jones and Matthias Tamm

[2.2]Paracyclophane derived bisphosphines for the activation of hydrogen by FLPs: application in domino hydrosilylation/hydrogenation of enones
Lutz Greb, Pascual Oña-Burgos, Adam Kubas, Florian C. Falk, Frank Breher, Karin Fink and Jan Paradies

This HOT paper by Ian Dance, from the University of New South Wales, reports on the mechanism of proton relay in nitrogenase enzymes.  The proton relay from the protein surface to a key sulfur atom of the FeMo-cofactor plays a core role in many of nitrogenase’s chemical mechanisms.

The water chain in nitrogenase is comparable with the purported proton pumping pathway of cytochrome c oxidase.

To read more about the detailed analysis of this mechanism you can download the full paper below…

The controlled relay of multiple protons required at the active site of nitrogenase
Ian Dance
Dalton Trans., 2012
DOI: 10.1039/C2DT30518F

Here are some of Ian Dance’s other recent Dalton Transactions publications:

Ramifications of C-centering rather than N-centering of the active site FeMo-co of the enzyme nitrogenase
Ian Dance
Dalton Trans., 2012,41, 4859-4865
DOI: 10.1039/C2DT00049K, Paper

Calculated vibrational frequencies for FeMo-co, the active site of nitrogenase, bearing hydrogen atoms and carbon monoxide
Ian Dance
Dalton Trans., 2011,40, 6480-6489
DOI: 10.1039/C1DT10505A, Paper

How does vanadium nitrogenase reduce CO to hydrocarbons?
Ian Dance
Dalton Trans., 2011,40, 5516-5527
DOI: 10.1039/C1DT10240K, Paper

Mimicking nitrogenase
Ian Dance
Dalton Trans., 2010,39, 2972-2983
DOI: 10.1039/B922606K, Perspective
From themed issue Bioinspired catalysis

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The team expected the assembly to form a helicate rather than catenate structure

Predicting the structure of large self-assembled units can become very complicated very quickly. Yet it is important for the rational design of new structures to understand how they assemble so new arrangements can be designed, with functional and valuable properties.

This Hot Article from the Piguet group investigates whether a pyridyl-benzimidazole ligand forms a double stranded helicate or a catenated architecture. The thermodynamic approach used to investigate the structures throws up some interesting results.

Looking for the origin of the switch between coordination-captured helicates and catenates
Lilit Aboshyan-Sorgho, Martine Cantuel, Gérald Bernardinelli and Claude Piguet
DOI: 10.1039/C2DT30414G

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The solution structure of the Th(IV)-hydroxo pentamer

Read more for FREE for 4 weeks at:
Thorium nanochemistry: the solution structure of the Th(IV)–hydroxo pentamer
Clemens Walther, Jörg Rothe, Bernd Schimmelpfennig and Markus Fuss
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT30243H 

Also of interest may be:
Infrared spectra and structures of the Th(OH)₂ and Th(OH)₄ molecules
Xuefeng Wang and Lester Andrews
Phys. Chem. Chem. Phys., 2005,7, 3834-3838
DOI: 10.1039/B509401A