0000000000285888
AUTHOR
Tom Bajorek
Bonding Trends in Lewis Acid Adducts of S4N4 — X-Ray Structure of TeCl4×S4N4.
Tetrasulfur tetranitride and tellurium tetrachloride react in dichloromethane to form a 1:1 adduct TeCl4·S4N4 (1). The crystal structure of 1 shows that TeCl4 is bonded to the S4N4 ring through a Te–N linkage. As a consequence, the transannular S···S bonds in S4N4 are broken and the molecule assumes an open, monocyclic conformation. The Te–N bond of 2.16(1) A is slightly longer than the single bond. The S–N bonds span a range of 1.55(1)–1.67(1) A. The adduct 1 was also characterized by mass spectrometry and Raman spectroscopy. The bonding and spectroscopic properties of 1 are compared by DFT calculations at the B3PW91/(RLC ECP) level of theory with those of BF3·S4N4 (2), SO3·S4N4 (3), AsF5·…
Bonding Trends in Lewis Acid Adducts of S 4 N 4 – X‐ray Structure of TeCl 4 ·S 4 N 4
Tetrasulfur tetranitride and tellurium tetrachloride react in dichloromethane to form a 1:1 adduct TeCl4·S4N4 (1). The crystal structure of 1 shows that TeCl4 is bonded to the S4N4 ring through a Te–N linkage. As a consequence, the transannular S···S bonds in S4N4 are broken and the molecule assumes an open, monocyclic conformation. The Te–N bond of 2.16(1) A is slightly longer than the single bond. The S–N bonds span a range of 1.55(1)–1.67(1) A. The adduct 1 was also characterized by mass spectrometry and Raman spectroscopy. The bonding and spectroscopic properties of 1 are compared by DFT calculations at the B3PW91/(RLC ECP) level of theory with those of BF3·S4N4 (2), SO3·S4N4 (3), AsF5·…
Isomerism in [MCl2(ERR‘)2] (M = Pd, Pt; E = S, Se; R, R‘ = Me, Ph)
A series of thioether and selenoether complexes [MCl2(EPh2)2] and [MCl2(SMePh)2] (M = Pt, Pd; E = S, Se) have been prepared and characterized to explore the isomerism of the complexes in solution and in the solid state. The NMR spectroscopic information indicates that only one isomer is present in solution in case of the palladium complexes, while two isomers are formed in the case of most platinum complexes. Single-crystal X-ray structures of trans-[PdCl2(SPh2)2] (1t), trans-[PdCl2(SePh2)2] (2t), cis-[PtCl2(SePh2)2] (4c), trans-[PdCl2(SMePh)2] (5t), and trans-[PtCl2(SMePh)2] (7t) are reported and have been used as starting points for the X-ray powder diffraction structure determinations us…
Experimental and computational investigation on the formation pathway of [RuCl2(CO)2(ERR′)2] (E = S, Se, Te; R, R′ = Me, Ph) from [RuCl2(CO)3]2 and ERR′
The pathways to the formation of the series of [RuCl2(CO)2(ERR′)2] (E = S, Se, Te; R, R′ = Me, Ph) complexes from [RuCl2(CO)3]2 and ERR′ have been explored experimentally in THF and CH2Cl2, and computationally by PBE0-D3/def2-TZVP calculations. The end-products and some reaction intermediates have been isolated and identified by NMR spectroscopy, and their crystal structures have been determined by X-ray diffraction. The relative stabilities of the [RuCl2(CO)2(ERR′)2] isomers follow the order cct > ccc > tcc > ttt ≈ ctc (the terms c/t refer to cis/trans arrangement of the ligands in the order of Cl, CO, and ERR′). The yields were rather similar in both solvents, but the reactions were signi…