Dalton Transactions Blog

December 2015’s HOT articles are here and free to access. These have also been compiled into a collection on our website.

Switching the orientation of Jahn–Teller axes in oxime-based MnIII dimers and its effect upon magnetic exchange: a combined experimental and theoretical study
Priyanka Comar, Thayalan Rajeshkumar, Gary S. Nichol, Mateusz B. Pitak, Simon J. Coles, Gopalan Rajaraman and Euan K. Brechin
Dalton Trans., 2015, 44, 19805-19811
DOI: 10.1039/C5DT03615A

Free to access until 23^rd December 2015

Coordination chemistry of 2,2′-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu
Joseph A. Macor, Jessie L. Brown, Justin N. Cross, Scott R. Daly, Andrew J. Gaunt, Gregory S. Girolami, Michael T. Janicke, Stosh A. Kozimor, Mary P. Neu, Angela C. Olson, Sean D. Reilly and Brian L. Scott
Dalton Trans., 2015, 44, 18923-18936
DOI: 10.1039/C5DT02976G

Free to access until 23^rd December 2015

Mechanistic features of the copper-free Sonogashira reaction from ESI-MS
Zohrab Ahmadi, Lars P. E. Yunker, Allen G. Oliver and J. Scott McIndoe
Dalton Trans., 2015, 44, 20367-20375
DOI: 10.1039/C5DT02889B

Free to access until 23^rd December 2015

First structural characterization of Pa(IV) in aqueous solution and quantum chemical investigations of the tetravalent actinides up to Bk(IV): the evidence of a curium break
Nidhu lal Banik, Valérie Vallet, Florent Réal, Réda Mohamed Belmecheri, Bernd Schimmelpfennig, Jörg Rothe, Rémi Marsac, Patric Lindqvist-Reis, Clemens Walther, Melissa A. Denecke and Christian M. Marquardt
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03560K

Free to access until 23^rd December 2015

Compositional dependence of anomalous thermal expansion in perovskite-like ABX3 formates
Ines E. Collings, Joshua A. Hill, Andrew B. Cairns, Richard I. Cooper, Amber L. Thompson, Julia E. Parker, Chiu C. Tang and Andrew L. Goodwin
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03263F

Free to access until 23^rd December 2015

Modular solid-phase synthesis, catalytic application and efficient recycling of supported phosphine–phosphite ligand libraries
Frank J. L. Heutz and Paul C. J. Kamer
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03226A

Free to access until 23^rd December 2015

Synthesis and controlled growth of osmium nanoparticles by electron irradiation
Anaïs Pitto-Barry, Luis M. A. Perdigao, Marc Walker, James Lawrence, Giovanni Costantini, Peter J. Sadler and Nicolas P. E. Barry
Dalton Trans., 2015, 44, 20308-20311
DOI: 10.1039/C5DT03205A

Free to access until 23^rd December 2015

Palladium(II) complexes featuring a mixed phosphine–pyridine–iminophosphorane pincer ligand: synthesis and reactivity
Thibault Cheisson and Audrey Auffrant
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT02789F

Free to access until 23^rd December 2015

Explaining the mechanical mechanisms of zeolitic metal–organic frameworks: revealing auxeticity and anomalous elasticity
Matthew. R. Ryder and Jin-Chong Tan
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03514G

Free to access until 23^rd December 2015

The structures of CyMe4-BTBP complexes of americium(III) and europium(III) in solvents used in solvent extraction, explaining their separation properties
Christian Ekberg, Elin Löfström-Engdahl, Emma Aneheim, Mark R. StJ. Foreman, Andreas Geist, Daniel Lundberg, Melissa Denecke and Ingmar Persson
Dalton Trans., 2015, 44, 18395-18402
DOI: 10.1039/C5DT02859K

Free to access until 23^rd December 2015

Stepwise assembly of mixed-metal coordination cages containing both kinetically inert and kinetically labile metal ions: introduction of metal-centred redox and photophysical activity at specific sites
Ashley B. Wragg, Alexander J. Metherell, William Cullen and Michael D. Ward
Dalton Trans., 2015, 44, 17939-17949
DOI: 10.1039/C5DT02957K

Free to access until 23^rd December 2015

Tin sulfide and selenide clusters soluble in organic solvents with the core structures of Sn4S6 and Sn4Se6
Mingdong Zhong, Zhi Yang, Yafei Yi, Dongxiang Zhang, Kening Sun, Herbert W. Roesky and Ying Yang
Dalton Trans., 2015, 44, 19800-19804
DOI: 10.1039/C5DT03244J

Free to access until 23^rd December 2015

HOT articles for October are below and free to acess for 4 weeks. These have also been compiled into a collection on our website.

Phosphole formation by 1,1-carboboration – reactions of bis-alkynyl phosphanes with a frustrated P/B Lewis pair
Annika Klose, Gerald Kehr, Constantin G. Daniliuc and Gerhard Erker
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03055B

Free to access until 5^th November 2015

The carboboration of Me₃Si-substituted alkynes and allenes with boranes and borocations
James R. Lawson, Valerio Fasano, Jessica Cid, Inigo Vitorica-Yrezabal and Michael J. Ingleson
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03003J

Free to access until 5^th November 2015

Transition metal-mediated donor–acceptor coordination of low-oxidation state Group 14 element halides
Anindya K. Swarnakar, Michael J. Ferguson, Robert McDonald and Eric Rivard
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03018H

Free to access until 5^th November 2015

September’s selection of HOT articles are below. These are free to acess for 4 weeks and available for viewing in a collection on our website.

Coordination polymers from a highly flexible alkyldiamine-derived ligand: structure, magnetism and gas adsorption studies
Chris S. Hawes, Nicholas F. Chilton, Boujemaa Moubaraki, Gregory P. Knowles, Alan L. Chaffee, Keith S. Murray, Stuart R. Batten and David R. Turner
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT02323H

Free to access until 16^th October 2015

Dinuclear iridium and rhodium complexes with bridging arylimidazolide-N3,C2 ligands: synthetic, structural, reactivity, electrochemical and spectroscopic studies
Fan He, Laurent Ruhlmann, Jean-Paul Gisselbrecht, Sylvie Choua, Maylis Orio, Marcel Wesolek, Andreas A. Danopoulos and Pierre Braunstein
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT02403J

Free to access until 16^th October 2015

Elucidating the mechanism responsible for anomalous thermal expansion in a metal–organic framework
Dewald P. van Heerden, Catharine Esterhuysen and Leonard J. Barbour
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT01927C

Free to access until 16^th October 2015

Polyfluorinated carba-closo-dodecaboranes with amino and ammonio substituents bonded to boron
Szymon Z. Konieczka, Michael Drisch, Katharina Edkins, Michael Hailmann and Maik Finze
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT02055G

Free to access until 16^th October 2015

Albumin binding and ligand-exchange processes of the Ru(III) anticancer agent NAMI-A and its bis-DMSO analogue determined by ENDOR spectroscopy
Michael I. Webb and Charles J. Walsby
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT02021B

Free to access until 16^th October 2015

Synthetic strategies to bicyclic tetraphosphanes using P1, P2 and P4 building blocks
Jonas Bresien, Kirill Faust, Christian Hering-Junghans, Julia Rothe, Axel Schulz and Alexander Villinger
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT02757H

Free to access until 16^th October 2015

Take a look at our HOT articles for July. These are only free to acess for 4 weeks only and are available for viewing in a collection on our website.

A mononuclear Ni(II) complex: a field induced single-molecule magnet showing two slow relaxation processes
Jozef Miklovič, Dušan Valigura, Roman Boča and Ján Titiš
Dalton Trans., 2015, 44, 12484-12487
DOI: 10.1039/C5DT01213A

Free to access until 6^th August 2015 

 Zn^II and Hg^II binding to a designed peptide that accommodates different coordination geometries
Dániel Szunyogh, Béla Gyurcsik, Flemming H. Larsen, Monika Stachura, Peter W. Thulstrup, Lars Hemmingsen and Attila Jancsó
Dalton Trans., 2015, 44, 12576-12588
DOI: 10.1039/C5DT00945F 

Free to access until 6^th August 2015  

Photophysical tuning of the aggregation-induced emission of a series of para-substituted aryl bis(imino)acenaphthene zinc complexes
Daniel A. Evans, Lucia Myongwon Lee, Ignacio Vargas-Baca and Alan H. Cowley
Dalton Trans., 2015, 44, 11984-11996
DOI: 10.1039/C5DT01529D 

Free to access until 6^th August 2015

An investigation into the photochemistry of, and the electrochemically induced CO-loss from, [(CO)₅MC(OMe)Me](M = Cr or W) using low-temperature matrix isolation, picosecond infrared spectroscopy, cyclic voltammetry, and time-dependent density functional theory 
Suzanne McMahon, Saeed Amirjalayer, Wybren J. Buma, Yvonne Halpin, Conor Long, A. Denise Rooney, Sander Woutersen and Mary T. Pryce
Dalton Trans., 2015, Advance Article 
DOI: 10.1039/C5DT01568E

Free to access until 6^th August 2015

Aza-macrocyclic complexes of the Group 1 cations – synthesis, structures and density functional theory study
John Dyke, William Levason, Mark E. Light, David Pugh, Gillian Reid, Hanusha Bhakhoa, Ponnadurai Ramasami and Lydia Rhyman  
Dalton Trans., 2015, Advance Article  
DOI: 10.1039/C5DT01865J  

Free to access until 6^th August 2015

As-stereogenic C2-symmetric organoarsines: synthesis and enantioselective self-assembly into a dinuclear triple-stranded helicate with copper iodide
Hiroki Adachi, Hiroaki Imoto, Seiji Watase, Kimihiro Matsukawa and Kensuke Naka 
Dalton Trans., 2015, Advance Article  
DOI: 10.1039/C5DT01490E  

Free to access until 6^th August 2015

Take a look at our HOT articles for May. These are only free to acess for 4 weeks only and are available for viewing in a collection on our website. 

Synthesis of CuInS₂ nanocrystals from a molecular complex – characterization of the orthorhombic domain structure
Jorge L. Cholula-Díaz, Gerald Wagner, Dirk Friedrich, Oliver Oeckler and Harald Krautscheid
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00419E

Free to access until 30^th June 2015

A cascade approach to hetero-pentanuclear manganese-oxide clusters in polyoxometalates and their single-molecule magnet properties
Kosuke Suzuki, Rinta Sato, Takuo Minato, Masahiro Shinoe, Kazuya Yamaguchi and Noritaka Mizuno
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT01363A

Free to access until 30^th June 2015

Quantum chemical and solution phase evaluation of metallocenes as reducing agents for the prospective atomic layer deposition of copper
Gangotri Dey, Jacqueline S. Wrench, Dirk J. Hagen, Lynette Keeney and Simon D. Elliott
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00922G

Free to access until 16^th June 2015

Synthesis of copper ion incorporated horseradish peroxidase-based hybrid nanoflowers for enhanced catalytic activity and stability
Burcu Somturk, Mehmet Hancer, Ismail Ocsoy and Nalan Özdemir
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT01250C

Free to access until 16^th June 2015

Platinum carbon bond formation via Cu(I) catalyzed Stille-type transmetallation: reaction scope and spectroscopic study of platinum-arylene complexes
Ali S. Gundogan, Xiangli Meng, Russell W. Winkel and Kirk S. Schanze
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00538H

Free to access until 16^th June 2015

Exceptionally rapid CO release from a manganese(I) tricarbonyl complex derived from bis(4-chloro-phenylimino)acenaphthene upon exposure to visible light
Samantha J. Carrington, Indranil Chakraborty and Pradip K. Mascharak
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT01007A

Free to access until 16^th June 2015

5-(Fluorodinitromethyl)-2H-tetrazole and its tetrazolates – Preparation and Characterization of New High Energy Compounds
Ralf Haiges and Karl O. Christe
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00291E 

Free to access until 25^th May 2015

Synthesis of magnesium ZIF-8 from Mg(BH4)2
S. Horike, K. Kadota, T. Itakura, M. Inukai and S. Kitagawa
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT01183C 

Free to access until 25^th May 2015

16-Electron pentadienyl- and cyclopentadienyl-ruthenium half-sandwich complexes with bis(imidazol-2-imine) ligands and their use in catalytic transfer hydrogenation
Thomas Glöge, Kristof Jess, Thomas Bannenberg, Peter G. Jones, Nadine Langenscheidt-Dabringhausen, Albrecht Salzer and Matthias Tamm
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT01080B 

Free to access until 25^th May 2015 

Structural and electronic characterization of multi-electron reduced naphthalene (BIAN) cobaloximes
Owen M. Williams, Alan H. Cowley and Michael J. Rose
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00924C 

Free to access until 25^th May 2015

Take a look at HOT articles for March. These are only free to acess for 4 weeks only and are available for viewing in a collection on our website.

An ionic liquid process for mercury removal from natural gas
Mahpuzah Abai, Martin P. Atkins, Amiruddin Hassan, John D. Holbrey, Yongcheun Kuah, Peter Nockemann, Alexander A. Oliferenko, Natalia V. Plechkova, Syamzari Rafeen, Adam A. Rahman, Rafin Ramli, Shahidah M. Shariff, Kenneth R. Seddon, Geetha Srinivasan and Yiran Zou  
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03273J

Free to access until 24^th April 2015

Relationship between crystal structure and thermo-mechanical properties of kaolinite clay: beyond standard density functional theory
Philippe F. Weck, Eunja Kim and Carlos F. Jové-Colón 
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00590F

Free to access until 23^rd April 2015

The titanium tris-anilide cation [Ti(N[^tBu]Ar)₃]⁺ stabilized as its perfluoro-tetra-phenylborate salt: structural characterization and synthesis in connection with redox activity of 4,4′-bipyridine dititanium complexes
Heather A. Spinney, Christopher R. Clough and Christopher C. Cummins
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00105F

Free to access until 14^th April 2015

Iridium–bipyridine periodic mesoporous organosilica catalyzed direct C–H borylation using a pinacolborane
Yoshifumi Maegawa and Shinji Inagaki
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C5DT00239G

Free to access until 14^th April 2015

“My original intention in the late 1940s was to spend a few years understanding the boranes, and then to discover a systematic valence description of the vast numbers of electron deficient intermetallic compounds. I have made little progress toward this latter objective,” said the late Professor William N. Lipscomb in his 1976 Nobel acceptance speech.¹

In their recent Dalton Transactions Hot Article, Jose M. Goicoechea and John E. McGrady examine the chemistry of main group cluster-encapsulated transition metal atoms, laying another piece of the foundation of Lipscomb’s “latter objective.”

The authors assign themselves an ambitious task: to provide a system to predict the geometries of cages of the tetrel elements (C, Si, Ge, Sn, Pb) which encapsulate transition metal atoms.  They focus on six high-symmetry cage structures, shown below, which have been observed for tetrel-encapsulated metal atoms (denoted M@E_x, for example Ni@Ge₁₂.).

The six three-dimensional cage geometries examined.

Lipscomb’s elegantly-described closo, nido, and arachno borane structures (“closed,”“nest”, and “spider’s web,” respectively) provided an initial basis for classifications of cages.  Later, the Wade/Mingos rules laid the foundation for predicting the geometries based on the electronic structure of the cluster.

Goicoechea and McGrady use the total valence electron count –  of the tetrel cages, plus the d-electron count of the encapsulated metal – to describe patterns in the structures.  Nevertheless, some results defy electron-count classification, for example, the preference of silicon cages to form D_6h-symmetric hexagonal prisms in M@Si₁₂ complexes, in contrast to the M@Ge₁₂ analogues.

It is a broad, big-picture paper, a synthesis of a wide range of experimental and theoretical results.  Some structures are known experimentally from x-ray crystallography, some have only been predicted computationally.  The authors discuss the varying relevance of considering the d-electron counts of the metals, and technological implications such as quenching of the magnetic moment of encapsulated metal atoms.  For me, the scope alone made this a worthwhile read.

Read the full article now:

On the structural landscape in endohedral silicon and germanium clusters, M@Si₁₂ and M@Ge₁₂
José M. Goicoechea and John E. McGrady
Dalton Trans., 2015, DOI: 10.1039/C4DT03573A

¹ Lipscomb, W.N. “The Boranes and Their Relatives” in Les Prix Nobel en 1976. Imprimerie Royal PA Norstedt & Soner, Stockholm, 1977

Ian Mallov is currently a Ph.D. student in Professor Doug Stephan’s group at the University of Toronto. His research is focused on synthesizing new Lewis-acidic compounds active in Frustrated Lewis Pair chemistry. He grew up in Truro, Nova Scotia and graduated from Dalhousie University and the University of Ottawa, and worked in chemical analysis in industry for three years before returning to grad school.

This month brings some more HOT articles. These are only free to acess for 4 weeks only and are available for viewing on our website.

Thermoelectric properties of the Zintl phases Yb₅M₂Sb₆ (M = Al, Ga, In)
Umut Aydemir, Alex Zevalkink, Alim Ormeci, Heng Wang, Saneyuki Ohno, Sabah Bux and G. Jeffrey Snyder
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03773A

Free to access until 25^th March 2015

Exploring excited states of Pt(II) diimine catecholates for photoinduced charge separation
Paul A. Scattergood, Patricia Jesus, Harry Adams, Milan Delor, Igor V. Sazanovich, Hugh D. Burrows, Carlos Serpa and Julia A. Weinstein
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03466J

Free to access until 25^th March 2015

On the structural landscape in endohedral silicon and germanium clusters, M@Si₁₂ and M@Ge₁₂
José M. Goicoechea and John E. McGrady
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03573A

Free to access until 9^th March 2015

The synthesis, structure, topology and catalytic application of a novel cubane-based copper(II) metal–organic framework derived from a flexible amido tripodal acid
Anirban Karmakar, Clive L. Oliver, Somnath Roy and Lars Öhrström
Dalton Trans., 2015, Advance Article
DOI: 10.1039/C4DT03087G

Free to access until 9^th March 2015