13 Aug 14:57
by Daichi Uchida,
Mariko Yukimoto,
Norihiro Tokitoh,
Mitsuaki Yamauchi,
Hiroko Yamada,
Yoshiyuki Mizuhata
We report the properties and reactivity of an unprecedented methylene-bridged 1,3-bis(germylene) derivative. In the solid state, the 1,3-bis(germylene) derivative undergoes dimerization to afford a 1,2,4,5-tetragermacyclohexa-1,4-diene (Ge4CHD) derivative. Moreover, the reactivity revealed that the Ge4CHD derivative dissociated into the methylene-bridged 1,3-bis(germylene) derivative in solution.
Abstract
We report the properties and reactivity of an unprecedented methylene-bridged 1,3-bis(germylene) derivative. In the solid state, it undergoes dimerization to afford a 1,2,4,5-tetragermacyclohexa-1,4-diene derivative (Ge4CHD). Moreover, theoretical calculations on Ge4CHD reveal σ*–π interactions between the two π orbitals (Ge═Ge) and the CH σ* orbital. This interaction is confirmed by a significant red shift in the solid-state UV–vis spectrum. In contrast to the behavior in the solid state, the Ge4CHD derivative dissociates in solution into a methylene-bridged 1,3-bis(germylene) derivative. The resultant 1,3-bis(germylene) derivative reacted with S8 to form a novel cage compound containing three S and two Ge atoms. On the other hand, in the reaction with triphenylphosphine sulfide, the in situ generated 2-thia-1,3-digermabicyclo[1.1.0]butane derivative activated the benzene solvent, leading to the formation of a [2 + 2] cycloaddition product. Additionally, the 1,3-bis(germylene) derivative reacted with 4-dimethylaminopyridine (DMAP) to form a three-membered ring. Its structural parameters and the results of theoretical calculations indicated the zwitterionic character.
16 Jul 10:14
by Manu Adhikari,
Sandeep Kumar Thakur,
Ashim Tamuli,
Manisha Kumari,
Ashwini K. Phukan,
Sanjay Singh
This study deals with the syntheses, isolation, and characterization of tricoordinate bicyclic (alkyl)(amino)carbene (BICAAC) adducts with germylene and stannylene halides. Subsequent KC8 reduction of BICAAC-germylene adducts afforded a bent (BICAAC)2Ge(0) species and a BICAAC stabilized trans-bent (Ge═Ge) digermanium complex. The reactivity of BICAAC-SnX2 adducts were investigated toward complexation with Fe2(CO)9, which afforded the corresponding donor-acceptor (Sn→Fe) metal adducts.
Abstract
Herein, we have disclosed the successful isolation and spectroscopic characterization of a series of bicyclic (alkyl)(amino) carbene (Me/iPrBICAAC) complexes of GeCl2 and SnX2; [MeBICAAC-GeCl2 (1); iPrBICAAC-GeCl2 (2); MeBICAAC-SnX2 (X = Cl (3); X = Br, (4))]. The in-situ KC8 reduction of GeCl2·dioxane in the presence of MeBICAAC led to the isolation of a zero-valent di-coordinated germylone [(MeBICAAC)2Ge] (5), whereas the reduction of adduct 2 afforded a trans-bent digermanium complex, [iPrBICAAC→Ge═Ge←iPrBICAAC] (6), having a Ge═Ge (2.3652(5) Å) double bond. Additionally, complexes 3 and 4 were reacted with diironnonacarbonyl Fe2(CO)9 to produce the corresponding Sn→Fe adducts 7 and 8, respectively. Further, attempts were made to convert the MeBICAAC-Sn adducts 3 and 4 to the corresponding tin-hydride complex, by treatment with LiBH4, however, in both the attempts, uncontrolled hydrogenation occurred to give the dihydrogented MeBICAAC complex, MeBICAAC(H2) (9). The solid-state structures of compounds 1–8 have also been elucidated using single-crystal X-ray diffraction technique. Further, computational investigations were performed to explain the bonding situation in 3–8 that establishes the ylidone character of 5, and supports the formation of 7–8 via donation of the lone pair at Sn to the Fe center.
10 Jul 12:17
Dalton Trans., 2025, 54,10667-10672
DOI: 10.1039/D5DT00966A, Paper
Togo Anzai, Koh Sugamata, Shogo Morisako, Takahiro Sasamori
This study reports the synthesis and structural characterization of a stable dicoordinated organoaluminum cation.
The content of this RSS Feed (c) The Royal Society of Chemistry
10 Jul 12:14
Dalton Trans., 2025, 54,10890-10897
DOI: 10.1039/D5DT00957J, Paper
Open Access
Felix Kracht, Sophie Mayer, Cäcilia Maichle-Mössmer, Reiner Anwander
Homoleptic titanium pyrazolates reversibly insert carbon dioxide to afford carbamate complexes, featuring redox stability but also gradual transformation to Ti(IV)-oxo species.
The content of this RSS Feed (c) The Royal Society of Chemistry
25 Jun 13:31
by Marco Neder, Merle Arrowsmith, Lukas Endres, Cornelius Mihm, Samuel Nees, Rüdiger Bertermann, and Holger Braunschweig
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c06017
20 Jun 14:03
by Kristof M. Altus, M. Arif Sajjad, Stuart A. Macgregor, and Andrew S. Weller
Organometallics
DOI: 10.1021/acs.organomet.5c00112
20 Jun 13:56
by Kajal Balayan, Himanshu Sharma, Kumar Vanka, Rajesh G. Gonnade, and Sakya S. Sen
Organometallics
DOI: 10.1021/acs.organomet.5c00120
20 Jun 13:54
by Shyam Sundar Mothuku, Uwe Monkowius, and Marko Hapke
Organometallics
DOI: 10.1021/acs.organomet.5c00102
20 Jun 13:54
by David Bürgy, Clemens K. Blasius, Tim Bruckhoff, Jonas Maurmann, Hubert Wadepohl, Joachim Ballmann, and Lutz H. Gade
Organometallics
DOI: 10.1021/acs.organomet.5c00134
20 Jun 13:47
by Kouki Matsubara, Yuji Yamada, Ayane Tokushige, Aoi Sakamoto, Rion Hosokawa, and Yuji Koga
Organometallics
DOI: 10.1021/acs.organomet.5c00126
20 Jun 13:45
by Toheeb Oluokun, Addison Fraker, and Alex McSkimming
Organometallics
DOI: 10.1021/acs.organomet.5c00139
06 Jun 12:55
by Rahul Kumar Siwatch, Zheng Jie Glenn Ng, Jia-Jun Sean Lim, Zheng-Feng Zhang, Ming-Der Su, and Cheuk-Wai So
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c07275
03 Jun 14:04
by Tak Hin Wong, Paul Varava, Farzaneh Fadaei-Tirani, Rosario Scopelliti, and Kay Severin
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c04371
03 Jun 13:54
by Daniel Hupperich, Jaime Ponce-de-León, Ignacio Funes-Ardoiz, Theresa Sperger, and Franziska Schoenebeck
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c04407
22 May 10:41
by Stav Deri, Moran Feller, Shibaram Panda, Batya Blank, Mark A. Iron, Yael Diskin-Posner, Liat Avram, Linda J. W. Shimon, Rakesh Mondal, and Samer Gnaim
Journal of the American Chemical Society
DOI: 10.1021/jacs.4c15496
07 May 14:53
by Jan Lorkowski, Levan Gojiashvili, Patrick Yorkgitis, Delphine Pichon, Jakub Talcik, Milan Gembicky, Thierry Roisnel, Olivier Baslé, Rodolphe Jazzar, Marc Mauduit, and Guy Bertrand
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c05642
07 May 14:42
by Christoph Helling, David J. D. Wilson, and Cameron Jones
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c04320
07 May 12:12
by Rafał Kusy and Karol Grela
Chemical Reviews
DOI: 10.1021/acs.chemrev.4c00001
24 Apr 13:50
by Jan Lorkowski, Patrick Yorkgitis, Fanny Morvan, Jennifer Morvan, Nicolas Vanthuyne, Thierry Roisnel, Milan Gembicky, Guy Bertrand, Marc Mauduit, and Rodolphe Jazzar
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c03845
22 Apr 13:55
by Daniel Rütter, Nils Nöthling, Markus Leutzsch, Alexander A. Auer, and Alois Fürstner
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c02178
09 Apr 14:34
by Marcel Eilers, Kevin Schwitalla, Marc Schmidtmann, and Rüdiger Beckhaus
Organometallics
DOI: 10.1021/acs.organomet.5c00023
09 Apr 14:32
by Jacob S. Mohar, Mrinal Bhunia, Alexander L. Laughlin, Andrew Ozarowski, J. Krzystek, Taylor M. Keller, Michael R. Gau, Kyle M. Lancaster, Joshua Telser, and Daniel J. Mindiola
Journal of the American Chemical Society
DOI: 10.1021/jacs.4c12242
09 Apr 14:30
by Chenyang Hu, Maren Pink, and Jose M. Goicoechea
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c02865
04 Apr 07:14
by David E. Ryan, Jack T. Fuller, III, Evan A. Patrick, Jeremy D. Erickson, Amy L. Speelman, Timothy G. Carroll, Gregory K. Schenter, Bojana Ginovska, Simone Raugei, R. Morris Bullock, and Ba L. Tran
Journal of the American Chemical Society
DOI: 10.1021/jacs.4c17955
25 Mar 15:40
by Jussi Lundahl,
Laura English,
Jas S Ward,
Petra Vasko
Germylene Lewis acid and MecAAC Lewis base join forces to activate and capture CO2 in a “push-pull” Frustrated Lewis pair (FLP) fashion. Extensive experimental and computational efforts reveal the nature of the component interactions for further development of effective and transition metal free CO2-capture.
Abstract
A novel combination of an amido-stabilised chlorogermylene (RGeCl) and a cyclic (alkyl)(amino)carbene (cAAC) has been utilized in a frustrated Lewis pair-type reaction to activate and capture CO2. The synthesis, characterization, and reactivity studies accompanied by extensive computational input reveal “push-pull”-type interactions in the isolated CO2-captured compounds. Both the steric and electronic factors as well as the Lewis acidity/basicity are found to play an important role in the reactivity and ability of the FLPs to activate CO2. The results indicate that the covalent interaction between the cAAC carbene carbon and electrophilic CO2-carbon is too strong to facilitate further reduction or reactivity of the bound CO2-moiety. However, the interaction between the Lewis acidic Ge-species and the nucleophilic O-atom of CO2 shows that germylenes can be utilised as the Lewis acidic partner in FLP-type chemistry and small molecule activation.
25 Mar 13:51
by Ming Liu, Yan-Cong Chen, Arpan Mondal, Huan Wang, Ming-Liang Tong, Richard A. Layfield, and Fu-Sheng Guo
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c00707
21 Mar 08:40
by Philipp Dabringhaus, Andrew Molino, Noah D. McMillion, and Robert J. Gilliard, Jr
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c00236
19 Mar 15:45
by Ayu Afiqah Nasrullah, Malte Fischer, Fabian Dankert, Eszter Barath, and Christian Hering-Junghans
Organometallics
DOI: 10.1021/acs.organomet.5c00012
17 Mar 12:09
by Bernardo de Souza
We present GOAT, a new global optimization algorithm that hops over the potential energy surface until it finds the global minimum and conformational ensembles. The algorithm does not rely on molecular dynamics, which makes it useful to run even with hybrid DFT and deal with systems withs complicated electronic structures.
Abstract
In this work, we propose a new Global Optimization Algorithm (GOAT) for molecules and clusters of atoms and show how it can find the global energy minima for both systems without resorting to molecular dynamics (MD). This avoids the potential millions of time-consuming gradient calculations required by a long MD run. Because of that, it can be used with any regular quantum chemical method, even with the costlier hybrid DFT. We showcase its accuracy by running it on various systems, from organic molecules to water clusters, metal complexes, and metal nanoparticles, comparing it with state-of-the-art methods such as the Conformer-Rotamer Ensemble Sampling Tool (CREST). We also discuss its underlying theory and mechanisms for succeeding in challenging cases. GOAT is, in general, more efficient and accurate than previous algorithms in finding global minima and succeeds in cases where others cannot due to the free choice for the Potential Energy Surface (PES).
14 Mar 09:18
by Zichen Zhang, Kunlong Li, Minghao Huang, Ting Chen, and Jiliang Zhou
Journal of the American Chemical Society
DOI: 10.1021/jacs.5c01964
