Dalton Transactions

doi: 10.1039/D2DT90092Kpmid: N/A

doi: 10.1039/D2DT90093Apmid: N/A

Deka, Rajesh; Orthaber, Andreas

doi: 10.1039/d2dt00755jpmid: 35578901

The discovery of the first isolable N-heterocyclic carbene in 1991 ushered in a new era in coordination chemistry. The remarkable bonding properties of carbenes have led to their rapid proliferation as auxiliary ligands for a wide range of transition metals and main group elements. In the case of group 15, while carbene-stabilized nitrogen and phosphorus compounds are extensively studied, the scope of research has shrunk significantly from arsenic to bismuth. This is essentially attributed to the decrease in stability of the C–E bond upon descending the group. Even so, modulating the carbene backbone or introducing alternative synthetic strategies not only alleviates the stability issues but also offers promising results in terms of the bonding and reactivities of these compounds. The purpose of the present perspective is to provide a comprehensive overview of the origins and development of carbene chemistry of arsenic, antimony, and bismuth, as well as to highlight the future prospects of this field.

Bekyarova, Elena; Conley, Matthew P.

doi: 10.1039/d2dt00459cpmid: 35586978

Understanding how a ligand affects the steric and electronic properties of a metal is the cornerstone of the inorganic chemistry enterprise. What happens when the ligand is an extended surface? This question is central to the design and implementation of state-of-the-art functional materials containing transition metals. This perspective will describe how these two very different sets of extended surfaces can form well-defined coordination complexes with metals. In the Green formalism, functionalities on oxide surfaces react with inorganics to form species that contain X-type or LX-type interactions between the metal and the oxide. Carbon surfaces are neutral L-type ligands; this perspective focuses on carbons that donate six electrons to a metal. The nature of this interaction depends on the curvature, and thereby orbital overlap, between the metal and the extended π-system from the nanocarbon.

Patra, Sushree Aradhana; Dinda, Rupam; Das Pattanayak, Pratikshya; Mohapatra, Deepika

doi: 10.1039/d2dt00241hpmid: 35616613

This frontier article covers the recent advancements in ruthenium complex catalysed decarbonylation reactions of different types of carbonyl compounds and provides a direction towards the mechanistic understanding. The mechanistic pathways provide new strategies for the use of appropriate ruthenium-catalysts, increase the substrate scope, and help in the synthesis of new complexes having multiple functionalities. The content of the article is categorized on the basis of the use of substrates. The new challenges of the decarbonylation reaction depend on the development of new ruthenium-catalysts and the efficiency of the catalytic cycles. Therefore, this short review will give an overall idea about the progress in the field of ruthenium-complex catalysed decarbonylation, catalytic pathways, synthetic applications, and utilities of their products and side products.

Yang, Luming; Oppenheim, Julius J.; Dincă, Mircea

doi: 10.1039/d2dt01337apmid: 35612004

Reaction of 2,3,6,7,10,11-hexaaminotriphenylene hexahydrochloride (HATP·6HCl) and (TpPhNi)Cl (TpPh = tris(3,5-diphenyl-1-pyrazolyl)borate) produces the radical-bridged trinickel complex [(TpPhNi)3(HITP)] (HITP3−˙ = 2,3,6,7,10,11-hexaiminotriphenylene). Magnetic measurements and broken-symmetry density functional theory calculations reveal strong exchange coupling persisting at room temperature between HITP3−˙ and two of the three Ni2+ centers, a rare example of strong radical-mediated magnetic coupling in multimetallic complexes. These results demonstrate the potential of radical-bearing tritopic HITP ligands as building blocks for extended molecule-based magnetic materials.

Guo, Ruixin; Tang, Changcheng; Xia, Mingjun; Liu, Lijuan; Wang, Xiaoyang

doi: 10.1039/d2dt00799apmid: 35616547

A new non-centrosymmetric iodate crystal Sm3(IO3)9(HIO3)4 has been successfully synthesized by a hydrothermal method. The crystal structure is a three-dimensional network with samarium polyhedra linked by iodate groups. It shows a moderate second harmonic generation response of 1.1 KH2PO4 (KDP). The strongest emission in its luminescence spectrum is located at 600 nm under 403 nm excitation. Hence, Sm3(IO3)9(HIO3)4 is a potential orange laser material.

Qi, Siming; Ge, Fei; Han, Xiao; Cheng, Puxin; Shi, Rongchao; Liu, Chao; Zheng, Yongshen; Xin, Mingyang; Xu, Jialiang

doi: 10.1039/d2dt00925kpmid: 35621191

Chiral metal halides have shown great potential for application in next generation nonlinear optical (NLO) devices owing to their intrinsic non-centrosymmetry. However, the structures and properties of chiral hybrid indium halides have been rarely reported, especially when it comes to second-harmonic generation (SHG) in NLO. In this work, we have synthesized a pair of new zero-dimensional (0D) chiral hybrid indium halides, (R-MPEA)6InCl9 and (S-MPEA)6InCl9, and studied their NLO properties. The as-prepared chiral hybrid indium halides crystallize in non-centrosymmetric P3221 and P3121 space groups, respectively. NLO studies show that 0D chiral hybrid indium halide crystals exhibit strong SHG responses with high polarization ratio and high laser damage threshold (LDT). This work enriches the family of chiral hybrid metal halide materials and offers a feasible strategy for the targeted design and synthesis of intrinsically non-centrosymmetric metal halide materials for NLO applications.

Baranov, Mark; Polin, Libi; Leffler, Nitai; Leitus, Gregory; Shames, Alexander I.; Weinstock, Ira A.

doi: 10.1039/d2dt00971dpmid: 35593418

Utilizing the inherent ability of Lindquist-type hexaniobate cluster-anions, [Nb6O19]8, to serve as oxo-donor ligands in complexes with transition-metal cations, we report the synthesis and characterization of the first all-inorganic ferric wheel, Li48[(Nb6O19)8Fe8(OH)8]88H2O, comprised of eight Fe atoms linked by eight hexaniobate cluster-anion ligands. Bond valence sum analysis of the X-ray structure and the synthesis conditions themselves indicate that the Fe atoms are in the +3 oxidation state. This is confirmed by magnetic susceptibility and electron paramagnetic resonance (EPR) measurements which indicate the presence of high spin (S = 5/2) Fe(iii) ions. In addition, magnetic susceptibility measurements reveal long-range superexchange antiferromagnetic interactions between the hexaniobate-ligand separated Fe3+ ions (J = 0.22 cm1). More generally, the results suggest the use of hexaniobate cluster-anions as linkers in the synthesis of other two- or three-dimensional polyoxometalate framework structures.

Komarnicka, Urszula K.; Kozie, Sandra; Skrska-Stania, Agnieszka; Kyzio, Agnieszka; Tisato, Francesco

doi: 10.1039/d2dt01055kpmid: 35615959

Herein, we present the synthesis of new complexes based on ruthenium(ii) (Ru(6-p-cymene)Cl2PPh2CH2OH (RuPOH) and Ru(6-p-cymene)Cl2P(p-OCH3Ph)2CH2OH (RuMPOH)) and iridium(iii) (Ir(5-Cp*)Cl2P(p-OCH3Ph)2CH2OH (IrMPOH) and Ir(5-Cp*)Cl2PPh2CH2OH (IrPOH)) containing phosphine ligands with/without methoxy motifs on phenyl rings (P(p-OCH3Ph)2CH2OH (MPOH) and PPh2CH2OH (POH)). The complexes were characterized by mass spectrometry, NMR spectroscopy (1D: 1H, 13C{1H}, and 31P{1H} and 2D: HMQC, HMBC, and COSY NMR) and elemental analysis. All the complexes were structurally identified by single-crystal X-ray diffraction analysis. The Ru(ii) and Ir(iii) complexes have a typical piano-stool geometry with an 6-coordinated arene (RuII complexes) or 5-coordinated (IrIII compounds) and three additional sites of ligation occupied by two chloride ligands and the phosphine ligand. Oxidation of NADH to NAD+ with high efficiency was catalyzed by complexes containing P(p-OCH3Ph)2CH2OH (IrMPOH and RuMPOH). The catalytic property might have important future applications in biological and medical fields like production of reactive oxygen species (ROS). Furthermore, the redox activity of the complexes was confirmed by cyclic voltamperometry. Biochemical assays demonstrated the ability of Ir(iii) and Ru(ii) complexes to induce significant cytotoxicity in various cancer cell lines. Furthermore, we found that RuPOH and RuMPOH selectively inhibit the proliferation of skin cancer cells (WM266-4; IC50, after 24 h: av. 48.3 M; after 72 h: av. 10.2 M) while Ir(iii) complexes were found to be moderate against prostate cancer cells (DU145).