Dithiocarbamatocarboxylate (DTCC) Ligands-Building Blocks for Hard/Soft-Heterobimetallic Coordination Polymers.

Four zinc/platinum(II) heterobimetallic coordination polymers with dithiocarboxylate-functionalized carboxylate (DTCC) ligands were prepared by different synthetic approaches and characterized by elemental analyses, IR and NMR (1H, 13C, and 195Pt) spectroscopy, thermal analyses coupled with mass spectrometry (TG/DTA/MS), and single-crystal and powder X-ray diffraction studies. Sequential syntheses via the carboxylic acid substituted platinum dithiocarbamates and zinc acetate revealed crystalline products in good to excellent yields. One-pot preparations from potassium DTCC salts, K2PtCl4, and ZnCl2 led to comparable products, thus demonstrating the high selectivity of the two donor groups toward platinum(II) and zinc. [SSC-N(Me)CH2COO]2- and [SSC-N(CH2COO)(CH2COOH)]2-, DTCC ligands derived from sarcosine and iminodiacetic acid, respectively, were found to form planar zigzag chains with zinc and platinum(II) ions, while the use of the l-proline-derived ligand [SSC-NC4H7COO]2- results in a helical structure. In the case of [SSC-N(CH2COO)2]3-, two-dimensional arrays are formed. All compounds are thermally stable up to 240-400 °C under nitrogen.

Identification and quantification of cannabinol as a biomarker for local hemp retting in an ancient sedimentary record by HPTLC-ESI-MS.

Cannabis products have been used in various fields of everyday life for many centuries, and applications in folk medicine and textile production have been well-known for many centuries. For traditional textile production, hemp fibers were extracted from the stems by water retting in stagnant or slow-moving waters. During this procedure, parts of the plant material' among them phytocannabinoids' are released into the water. Cannabinol (CBN) is an important degradation product of the predominant phytocannabinoids found in Cannabis species. Thus, it is an excellent indicator for present as well as ancient hemp water retting. In this study, we developed and validated a simple and fast method for the determination of CBN in sediment samples using high-performance thin-layer chromatography (HPTLC) combined with electrospray ionization mass spectrometry (ESI-MS), thereby testing different extraction and cleanup procedures' as well as various sorbents and solvents for planar chromatography. This method shows a satisfactory overall analytical performance with an average recovery rate of 73%. Our protocol enabled qualitative and quantitative analyses of CBN in samples of a bottom sediment core' having been obtained from a small lake in Northern India, where intense local retting of hemp was suggested in the past. The analyses showed a maximum CBN content in pollen zone 4 covering a depth range of 262-209 cm, dating from approximately 480 BCE to 1050 CE. These findings correlate with existing records of Cannabis-type pollen. Thus, the method we propose is a helpful tool to track ancient hemp retting activities. Graphical Abstract.

A Tunable Trifluoromethyliodonium Reagent.

Four complexes of MCl4 (M=Ti, Zr, Hf) with the hypervalent trifluoromethyl iodine reagent trifluoromethyl-1,3-dihydro-3,3-dimethyl-1,2-benziodoxole (1,=L) are described. With TiCl4 , an I-O bond cleavage occurs, leading to the formation of the trifluoromethyliodonium alcoholate complexes [Ti2 Cl6 (L)4 ]Cl2 (2 a) and Ti2 Cl8 (L) (2 b). Reactions with ZrCl4 and HfCl4 form the complexes ZrCl4 (L)2 (3) and HfCl4 (L)2 (4), respectively, wherein the original I-O bond is retained and elongated compared to that in free 1. Therefore, the reactivity of 1 can be easily and practically fine-tuned by addition of different metal chlorides, following the order ZrCl4 /HfCl4

Aliovalent anion substitution as a design concept for heteroanionic Ruddlesden-Popper hydrides.

Substituting 2 O2- ⇒ N3- + H- in LiLa2HO3 yields dark-brown heteroanionic hydrides, which were synthesized by solid-state reactions from Li3N, LaH3 (and La2O3). They crystallize in the K2NiF4 type structure with mixed H/N sites in LiLa2N1.5H2.5 and with mixed N/O sites in LiLa2N0.84(6)H1.56(3)O1.16(6). The latter is a semiconductor with small band gap and partly covalent Li-H interaction.

Three new types of transition metal carboranylamidinate complexes.

Three new types of transition metal carboranylamidinate complexes are reported. The tetranuclear Mn(ii) complex Mn4Cl6[(o-C2B10H10)C(NiPr)(NHiPr)]2(THF)4·THF (2) was prepared by treatment of anhydrous MnCl2 with Li[(o-C2B10H10)C(NiPr)(NHiPr)] ([double bond, length as m-dash]Li[HLiPr]) in THF, while the analogous reaction with FeCl2 afforded ionic [Li(DME)3][FeCl2{(o-C2B10H10)C(NiPr)(NHiPr)}] (3). The dinuclear Mo(ii) complex Mo2[(o-C2B10H10)C(NiPr)(NHiPr)]2(OAc)2·2THF (4), obtained from Mo2(OAc)4 and 2 equiv. of Li[HLiPr], represents the first example of a M-M multiple bond stabilized by carboranylamidinate ligands. All title compounds were structurally characterized by single-crystal X-ray diffraction. The M-M bonding in compound 4 has been further elucidated through Complete Active Space Self Consistent Field (CASSCF) calculations.

High-yield synthesis of a unique Mn(iii) siloxide complex through KMnO4 oxidation of a Mn(ii) precursor.

A unique trivalent manganese siloxide complex, blue-violet MnIIILi2Cl[(Ph2SiO)2O]2(THF)4·2THF (3) has been prepared by a straightforward two-step synthetic protocol. Lithiation of (Ph2SiOH)2O (1) followed by reaction with MnCl2(THF)2 gave the structurally remarkable Mn(ii) precursor MnIILi4Cl2[(Ph2SiO)2O]2(THF)5·2THF (2). Surprisingly, the final oxidation step could be achieved using KMnO4 in THF to provide the Mn(iii) species 3 in high yield (91%). Both title compounds were structurally characterized by single-crystal X-ray diffraction.