Heteroatom-containing degradable polymers have strong potential as sustainable replacements for petrochemically derived materials. However, to accelerate and broaden their uptake greater structural diversity and new synthetic methodologies are required. Here...
Although a multitude of studies have explored the coordination chemistry of classical tripodal ligands containing a range of main-group bridgehead atoms or groups, it is not clear how periodic trends affect ligand character and reactivity within a single ligand family. A case in point is the extensive family of neutral tris-2-pyridyl ligands E(2-py) (E=C-R, N, P), which are closely related to archetypal tris-pyrazolyl borates. With the 6-methyl substituted ligands E(6-Me-2-py) (E=As, Sb, Bi) in hand, the effects of bridgehead modification alone on descending a single group in the periodic table were assessed. The primary influence on coordination behaviour is the increasing Lewis acidity (electropositivity) of the bridgehead atom as Group 15 is descended, which not only modulates the electron density on the pyridyl donor groups but also introduces the potential for anion selective coordination behaviour.
The polychloride salt [CCl(NMe2 )2 ](+) 2 [Cl8 ](2-) was synthesized and crystallized in the ionic liquid [BMP]OTf. The compound was fully characterized by Raman spectroscopy as well as X-ray single-crystal structure determination, and represents the first example of a polychloride dianion to be described. Detailed gas-phase and solid-state calculations concerning the nature of the bonding situation were also performed.
For decades the chemistry of polyhalides was dominated by polyiodides and more recently also by an increasing number of polybromides. However, apart from a few structures containing trichloride anions and a single report on an octachloride dianion, [Cl ] , polychlorine compounds such as polychloride anions are unknown. Herein, we report on the synthesis and investigation of large polychloride monoanions such as [Cl ] found in [AsPh ][Cl ], [PPh ][Cl ], and [PNP][Cl ]⋅Cl , and [Cl ] obtained in [PNP][Cl ]. The polychloride dianion [Cl ] has been obtained in [NMe Ph] [Cl ]. The novel compounds have been thoroughly characterized by NMR spectroscopy, single-crystal Raman spectroscopy, and single-crystal X-ray diffraction. The assignment of their spectra is supported by molecular and periodic solid-state quantum-chemical calculations.
The polybromide salts [BrC(NMe2)2]2[Br8] and [BrC(NMe2)2][Br3] were synthesized in the ionic liquid [BMP][OTf] (1‐butyl‐1‐methyl‐pyrrolidinium triflate). The compounds were characterized by Raman, NMR, and X‐ray single crystal structure determination as well as quantum‐chemical calculations. The polybromide dianion [Br8]2– structure shows similarities to the very recently reported structure of the first octachloride [Cl8]2–.
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