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Treatment of [Cp*TaCl SB 4 sb ] with chalcogen-ligated monoborate nucleophiles, [BH SB 3 sb (EPh)] SP - sp (E = S or Se) yielded various smaller borane analogues. Cover Feature: Metal Coordinated Tri- and Tetraborane Analogues (Eur. J. Inorg. Keywords: Boranes; Chalcogens; Metallaheteroboranes; Tantalum; Structure elucidation EN Boranes Chalcogens Metallaheteroboranes Tantalum Structure elucidation 4407 4407 1 11/24/21 20211122 NES 211122 B The Cover Feature b shows triborane and tetraborane analogues which are stabilized in the coordination sphere of tantalum atom(s). [Extracted from the article]

Boriranes, highly strained three-membered cyclic organoboron heterocycles, have emerged as potential synthons for the synthesis of many organoboron species. However, the synthesis of boriranes with tricoordinate, sp 2 -hybridised boron and tetracoordinate, sp 3 -hybridised carbon atoms is very challenging owing to their high Lewis acidity. Herein we describe the isolation of base-free triaminoboriranes from the room-temperature reaction of diaminoalkynes with an aminodistannylborane. Further elimination of stannyl groups from these boriranes using potassium graphite afforded 2π-aromatic triaminoborirenes. To our knowledge, these are the first examples of conversions of alkanes to alkenes using reducing agents. Interestingly, the triaminoborirene underwent photolytic ring opening to afford a boryl- and amino-substituted acetylene featuring a polarised alkynyl group.

Chlorinated polymers have made enormous contributions to materials science and are commercially produced on a large scale. These chlorinated polymers could be recycled as chlorine sources to efficiently produce valuable chlorinated compounds owing to their facile release of HCl. Although the thermal stability of PVDC is low compared to PVC, this can be advantageous in terms of easy and fast dehydrochlorination. Herein, we report an efficient electrochemical chlorination using poly(vinylidene chloride) (PVDC) as a chlorine source that works in an undivided cell and applies to a good number of examples. This method works on commodity polymers such as waste PVDC-PVC pharma blister film, PVDC-PO multilayer food packaging, and compression molded sheets of Ixan PVDC (with heat stabilizer) with similar efficiency. Furthermore, this method also provides the dechlorination of PVDC up to 98 %, leading to unsaturated dechlorinated material. Converting PVDC into more stable unsaturated compounds, the release of harmful chlorine-containing gases during incineration can be minimized. Additionally, this method is not only restricted to batch processes but an electroflow process for PVDC dechlorination and electrosynthesis has also been demonstrated., (© 2025 Wiley-VCH GmbH.)

Since the pioneering electron counting rule for borane clusters was proposed by Wade, the structures and bonding of boron clusters and their derivatives have been elegantly rationalised. However, this rule and its modified versions faced problems explaining the electronic structures of less spherical deltahedra, unlike the core geometries of borate dianions [B n H n ] 2- ( n = 6-12). Herein, we report the isolation of a series of osmaborane clusters [(Cp*Os) 2 B n H n ], 1-5, ( n = 6-10) by the thermolysis of an in situ generated intermediate, obtained from the rapid condensation of [Cp*OsBr 2 ] 2 and [LiBH 4 ·THF], with [BH 3 ·THF] or [BH 3 ·SMe 2 ]. Interestingly, all these clusters show unusual less spherical deltahedral shapes that can be generated from canonical [B n H n ] 2- ( n = 8-12) shapes by doing diamond-square-diamond (DSD) rearrangements. The DSD rearrangements led to the generation of higher degree vertices, which are occupied by Os atoms and also generated Os-Os bonds in these clusters. Theoretical calculations revealed that these Cp*Os⋯OsCp* interactions in clusters 1-5 played a crucial role in their structural shape and electron count. These less spherical deltahedral clusters are rare, and most significantly, clusters 1-5 with ( n -1) skeleton electron pairs (SEPs) do not follow Wade-Mingos electron counting rules and can be classified as hypoelectronic closo clusters., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The field of diborinane is sparsely explored area, and not many compounds are structurally characterized. The room-temperature reaction of [{Cp*RuCl(μ-Cl)} 2 ] (Cp* = η 5 -C 5 Me 5 ) with Na[BH 3 (SCHS)] yielded ruthenium dithioformato [{Cp*Ru(μ,η 3 -SCHS)} 2 ], 1, and 1-thioformyl-2,6-tetrahydro-1,3,5-trithia-2,6-diborinane complex, [(Cp*Ru){(η 2 -SCHS)CH 2 S 2 (BH 2 ) 2 }], 2. To investigate the reaction pathway for the formation of 2, we carried out the reaction of [(BH 2 ) 4 (CH 2 S 2 ) 2 ], 3, with 1 that yielded compound 2. To the best of our knowledge, it appears that compound 2 is the first example of a ruthenium diborinane complex where the central six-membered ring [CB 2 S 3 ] adopts the chair conformation. Furthermore, room temperature reaction of 1 with [BH 3 ·thf] resulted in the isolation of agostic-bis(σ-borate) complex, [Cp*Ru(μ-H) 2 BH(S-CH═S)], 4. Thermolysis of 4 with trace amount of tellurium powder led to formation of bis(bridging-boryl) complex, [{Cp*Ru(μ,η 2 -HBS 2 CH 2 )} 2 ], 5, via dimerization of 4 followed by dehydrogenation. Compound 5 can be considered as a bis(bridging-boryl) species, in which the boryl units are connected to two ruthenium atoms. Theoretical studies and chemical bonding analyses demonstrate the reason for exceptional reactivity and stability of these complexes.

Among the series of stable closo -borate dianions, [B n H n ] 2- , the X-ray crystallographic structure of [B 7 H 7 ] 2- was determined only in 2011. To explore its chemistry and stability, we have isolated and structurally characterized two new transition metal complexes of the heptaborane, [(Cp 2 M) 2 B 9 H 11 ] (Cp = η 5 -C 5 H 5 ; M = Zr or Hf). The structures of [(Cp 2 M) 2 B 9 H 11 ] contain a pentagonal bipyramidal B 7 core, coordinated by two {Cp 2 M} and two {BH 2 } units equatorially. Structural and spectroscopic characterizations and DFT calculations show that [(Cp 2 M) 2 B 9 H 11 ] complexes are substantially more stable than the parent dianion, in either [B 7 H 7 ] 2- or ( n Bu 4 N) 2 [B 7 H 7 ]. Our theoretical study and chemical bonding analyses reveal that the surprising stability of the two new heptaborane metal complexes is due to multi-center covalent bonds related to the two exo -{Cp 2 M} units, as well as electrostatic interactions between the {Cp 2 M} units and the B 7 core. The facile syntheses of the heptaborane metal-complexes will allow further exploration of their chemistry.