The Clar Structure in Inorganic BN Analogues of Polybenzenoid Hydrocarbons: Does it Exist or Not?

The Clar structure of polybenzenoid hydrocarbons (PBHs) have attracted considerable interest of both theoretical and experimental chemists since it was proposed in the 1950s. However, it remains unclear whether the Clar structure could exist in inorganic PBHs, the boron nitride (BN) analogues where the alternate boron and nitrogen atoms are used to replace the carbon atoms of PBHs. Here, we carry out thorough density functional theory (DFT) calculations to probe the possibility of Clar structures in BN analogues of PBHs.

Unexpected higher stabilisation of two classical antiaromatic frameworks with a ruthenium fragment compared to the osmium counterpart: origin probed by DFT calculations

Density functional theory (DFT) calculations were carried out to investigate the stability and aromaticity of metallapentalocyclobutadienes. The results reveal unexpected higher stabilisation achieved with a 3d ruthenium fragment compared to the 4d osmium counterpart. Moreover, direct 1–3 metal–carbon bonding in the metallabutadiene unit of these two complexes is negligible.

http://pubs.rsc.org/en/content/articlelanding/2015/cc/c5cc08291a#!divAbstract

Congratulations to Jingjing, Yulei, and Ke for their paper accepted in Chem. Commun.

Communication

Unexpected Higher Stabilisation of Two Classical Antiaromatic Frameworks with a Ruthenium Fragment over Osmium Counterpart: Origin Probed by DFT Calculations

Jingjing Wu,   Yulei Hao,   Ke An and   Jun Zhu  

Stability, Reactivity, Selectivity, Catalysis, and Predictions of 1,3,2,5-Diazadiborinine: Computational Insight into a Boron–Boron Frustrated Lewis Pair

Recent progress in frustrated Lewis pairs (FLPs) has attracted increasing attention. However, most of the FLPs are composed of Lewis basic phosphines and Lewis acidic boranes. In 2015, Kinjo and co-workers reported the first intramolecular boron–boron FLP, namely, 1,3,2,5-diazadiborinine (1), which showed high regioselectivity in the reactions with methyl trifluoromethansulfonate, phenylacetylene, and CO2. More interestingly, the activation of CO2 was found to be reversible when the temperature was elevated to 90 °C.

Five-Membered Cyclic Metal Carbyne: Synthesis of Osmapentalynes by the Reactions of Osmapentalene with Allene, Alkyne, and Alkene

The synthesis of small cyclic metal carbynes is challenging due to the large angle strain associated with the highly distorted nonlinear triple bonds. Herein, we report a general route for the synthesis of five-membered cyclic metal carbyne complexes, osmapentalynes, by the reactions of an osmapentalene derivative with allene, alkyne, and alkene. Experimental observations and theoretical calculations document the aromaticity in the fused five-membered rings of osmapentalynes.

Reactivity of Germylene toward Phosphorus-Containing Compounds: Nucleophilic Addition and Tautomerism

A series of phosphorus-substituted germanium(II) complexes, L1GeR [L1 = CH{(CMe)(2,6-iPr2C6H3N)}2; 2, R = PPh2; 4, R = OPPh2; 5a, R = OP(O)Ph2; 5b, R = OP(O) (OnBu)2; 6a, R = OP(S)Ph2; 6b, R = OP(S)(OEt)2], were synthesized through the direct activation of various organic phosphorus compounds by N-heterocyclic ylide-like germylene 1.

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