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The coordination capability of two N,C,N pincer coordinated stibinidenes, i. e. bis(imino)‐ [2,6‐(DippN=CH)2C6H3]Sb (1) or imino‐amino‐ [2‐(DippN=CH)‐6‐(DippNHCH2)C6H3]Sb (2) toward palladium(II) and platinum(II) centers was examined. In the course of this study, seven new square‐planar bis(stibinidene) complexes were synthesized and characterized by NMR, IR, Raman, UV‐vis spectroscopy and single crystal (sc)‐X‐ray diffraction analysis. In all cases, both stibinidene ligands 1 or 2 adopt trans positions, but differ significantly in the torsion angle describing mutual orientation of aromatic rings of the stibinidenes along the Sb−Pd/Pt−Sb axes. Furthermore, majority of complexes form isomers in solution most probably due to a hindered rotation around Sb−Pd/Pt bonds caused by bulkiness of 1 and 2. This phenomenon also seems to be influenced by the absence/presence of a pendant −CH2NH− group in 1/2 that is able to form intramolecular hydrogen bonds with the adjacent chlorine atom(s) attached to the metal centers. The whole problem was subjected to a theoretical study focusing on the role of hydrogen bonds in structure architecture of the complexes. To describe the UV‐vis spectra of these highly coloured complexes, TD‐DFT calculations were employed. These outline differences between the stibinidene ligands, the transition metals as well as between the charge of the complexes (neutral or anionic). [ABSTRACT FROM AUTHOR]

Aim: Worldwide, floras are becoming homogenized at global scales, but regional patterns vary. Here, we present the first assessment for the Malesian phytogeographical region in terms of the timing of introductions, direction, magnitude and drivers of floristic change due to alien plant naturalizations. Location: Malesian phytogeographic region, including Southeast Asia and the Pacific. Taxon: Tracheophyta (vascular plants). Methods: We compiled data on first records of naturalized plants in Malesia to investigate temporal trends in the rate and origin of introductions. We then calculated β‐diversity (including turnover and nestedness) for the native, naturalized and Anthropocene (native + naturalized) floras for each pair of island groups (36 pairs), and a homogenization index for the native and Anthropocene floras, using presence/absence data for 31,580 plant species. Mantel tests were used to investigate the geographic, climatic and anthropogenic correlates of dissimilarity and homogenization. Results: Around 75% of all naturalized species documented to date were already reported for the first time within Malesia prior to 1950. This has led to homogenization between the historic (native) and contemporary (Anthropocene) floras for all island group pairs. Turnover was the most important process for driving compositional dissimilarity between island groups in Malesia in the native and Anthropocene floras, but homogenization resulted from decreases in nestedness and turnover. Differences in average taxonomic homogenization for island groups were associated with differences in their level of anthropogenic modification. Main Conclusions: This study improves current understanding of the direction and drivers of floristic homogenization in one of the world's most diverse tropical regions. Alien plant introductions carry a long historical legacy in Malesia, and naturalizations of these plants have led to overall taxonomic homogenization of the region's flora. Expected increases in the magnitude of human modification, without appropriate policy, will likely lead to further reductions in the floristic uniqueness of island groups. [ABSTRACT FROM AUTHOR]

A set of N-coordinated tellurium(II) compounds containing either C,N-chelating ligands CNR (where CN = 2-(RN＝CH)C6H4, R = tBu or Dipp; Dipp = 2,6-iPr2C6H3) or N,C,N pincer ligands NCNR (where NCN = 2,6-(RN＝CH)2C6H4, R = tBu or Dipp) were synthesized. In the case of C,N-chelated compounds, the reaction of CNDippLi with Te(dtc)2 (where dtc = Et2NCS2) in a 1 : 1 molar ratio smoothly provided the carbamate CNDippTe(dtc) which upon treatment with 2 eq. of HCl provided the chloride CNDippTeCl. In contrast, the analogous conversion of NCNRLi with Te(dtc)2 surprisingly furnished ionic bromides [NCNRTe]Br as a result of the exchange of dtc by Br coming from nBuBr present in the reaction mixture. Furthermore, the reaction of CNDippTeCl or [NCNRTe]Br with silver salts AgX (X = OTf or SbF6) provided the expected tellurenium cations [CNDippTe]SbF6 and [NCNRTe]X. To further increase the Lewis acidity of the central atom, the oxidation of selected compounds with 1 eq. of SO2Cl2 was examined yielding stable compounds [CNtBuTeCl2]X and [NCNtBuTeCl2]X. The oxidation of the Dipp substituted compounds proved to be more challenging and an excess of SO2Cl2 was necessary to obtain the oxidized products [CNDippTeCl2]SbF6 and [NCNDippTeCl2]SbF6, which could solely be characterized in solution. Compounds [CNtBuTeCl2]OTf and [NCNtBuTeCl2]OTf were shown to undergo a controlled hydrolysis to the corresponding telluroxanes. All compounds were studied by multinuclear NMR spectroscopy in solution and for selected compounds solid state 125Te NMR spectroscopy and single-crystal X-ray diffraction analysis were performed. The Lewis acidity of the studied cations was examined by the Gutmann–Beckett method using Et3PO as the probing agent. The Te–N chalcogen bonding situation of selected compounds has also been examined computationally by a set of real-space bonding indicators. [ABSTRACT FROM AUTHOR]

The oxidative addition of CF3SO3CH2Si(CH3)3 (NpSiOTf) toward organopnictogen(I) N,C,N-pincer compounds, i.e. [2,6-(DippN＝CH)2C6H3]E (1-E, where E = Sb, Bi; Dipp = 2,6-iPr2C6H3) produced compounds [2,6-(DippN＝CH)2C6H3]E(NpSi)(OTf) (2-E, where E = Sb, Bi). By analogy, the in situ reduction of [2,6-(Me2NCH2)2C6H3]ECl2 (3-E, where E = Sb, Bi) followed by treatment with NpSiOTf or MeI gave compounds [2,6-(Me2NCH2)2C6H3]E(R)(X) (R/X = NpSi/OTf 4-E, where E = Sb, Bi; R/X = Me/I 5-Sb). The reactivity of these compounds toward 1 eq. of K[BEt3H] was examined showing remarkable differences depending both on the ligand backbone and the pnictogen used. Thus in the case of 2-E, the addition of the hydride across the imino-function was achieved thereby yielding azapnicta-heterocyclic compounds [2-(DippNCH2)-6-(DippN＝CH)C6H3]E(NpSi) (6-E, where E = Sb, Bi). The same reaction of 4-Bi produced dibismuthine {[2,6-(Me2NCH2)2C6H3]Bi(NpSi)}2 (7-Bi), but in the case of 4/5-Sb the analogous distibines {[2,6-(Me2NCH2)2C6H3]Sb(R)}2 (R = NpSi7-Sb, Me 8-Sb) were not formed directly and hydrides [2,6-(Me2NCH2)2C6H3]Sb(R)H (R = NpSi9-Sb, Me 10-Sb) could be isolated instead. Nevertheless, heating of both 9-Sb and 10-Sb led to an activation of a labile Sb–H bond and the formation of distibines 7/8-Sb. [ABSTRACT FROM AUTHOR]