[ReCl₂(NS)(NSCl)(Pyridin)₂], ein Thionitrosyl‐chlorthio‐nitrenkomplex des Rheniums

Abstract

Die Titelverbindung wird durch Umsetzung von Pyridin mit [ReCl3(NSCl)2POCl3] oder mit [ReCl3(NSCl)2]2 · (μ‐N2S2) unter der reduzierenden Wirkung von Dichlormethan erhalten. Sie ist in CH2Cl2 etwas löslich und kann daraus in Form schwarzer Einkristalle erhalten werden. Das IR‐Spektrum wird mitgeteilt. Nach der röntgenographischen Strukturbestimmung kristallisiert [ReCl2(NS)(NSCl)(Pyridin)2] in der Raumgruppe P21/c mit vier Formeleinheiten pro Elementarzelle; a = 1551,6, b = 694,9, c = 1513,2 pm, β = 96,50° (Verfeinerung bis R = 2,7% für 2105 beobachtete Reflexe). [ReCl2(NS)(NSCl)(Pyridin)2] bildet einen monomeren Molekülkomplex, in dem das Rhenium verzerrt oktaedrisch von zwei Chloratomen, von den N‐Atomen der beiden zueinander cis‐ständig angeordneten Liganden des Thionitrosyls und des Chlorthionitrens, sowie von den N‐Atomen der Pyridinmoleküle umgeben ist. In trans‐Position zur gestreckten ReNS‐Gruppe (176°) mit Bindungsabständen ReN von 177 pm und NS von 152 pm befindet sich eines der Pyridinmoleküle. In trans‐Stellung zum Chlorthionitrenliganden (Bindungswinkel ReNS = 159°, Abstände ReN = 189 pm und NS = 149 pm ist dagegen einer der Cl‐Liganden angeordnet).

Halogenation at a Dimolybdenum(V) and Ditungsten(V) Sulfur Bridge: Metallosulfenyl Halides M2(.mu.-SX) and [M2(.mu.-SX3)]n. Charge-Transfer Interactions

“…For twoor threecoordinate sulfur compounds, S-Br structural data have been reported wherein S is also bonded to C, Si, N, O, or another S. For the few which appear to contain discrete S-Br bonds, those bond lengths are in the range of 2.162(6)-2.255(5) Á.42•44•48•51-53 (Some of these were gas phase measurements.) The range broadens considerably to 2.136(5)-2.449(3) Á for those compounds which also contain charge transfer, ionic, or other contributory influences on the S-Br bond length.17 [54][55][56][57][58][59][60][61] For \V2SBr, there are no significant intermolecular interactions; the Br The structure of [M02SI3],, is substantially different from that of \V2SBr and from those of the prior molybdenum derivatives, 3. This is true of the M02 dimer portion itself and of the polymeric nature of the S-I-I-I-S link; these two results are presented separately.…”

Synthesis and Characterization of Osmium Nitrosyl Porphyrins Containing Organo, Halogeno, and μ-Oxo Ligands, and Extensions to the First Organometallic Thionitrosyl Porphyrin

“…Importantly, the M-N(S) bond lengths for other (nongroup 8) metal thionitrosyl complexes range from 1.694(2) (M ) Cr) 96 to 1.87(2) Å (M ) Re). 97 MN-S bond lengths for these nongroup 8 compounds range from 1.38(2) (M ) Re) 98 to 1.592(11) Å (M ) Mo), 99 whereas M-N-S bond angles range from 170.0(4)°(M ) Tc) 100 to 179.9(1)°(M ) Tc). 101 The spectroscopically pure (OEP)Os(NS)Me compound is generated in 23% yield from the reaction of (OEP)Os(NS)Cl with MeMgBr in THF.…”

A four-coordinate thionitrosyl complex of vanadium

“…Consequently, reports of structurally characterized early transition metal thionitrosyl complexes are rare compared to thionitrosyl complexes featuring 4d and 5d late transition metals. 2,[9][10][11][12][13][14][15][16][17] We sought to isolate such species directly from a vanadium nitride and elemental sulfur and chose the vanadium nitride [(nacnac)VRN(OAr)] 18 (nacnac À = [ArNC(CH 3 )] 2 CH, Ar = 2,6-i Pr 2 C 6 H 3 ), since the metal is in a lowcoordinate environment, and the nitride ligand that is formally in a V (V) RN (3À) should be charge-polarized enough to act as a strong nucleophile attacking sulfur. In this work we describe the first vanadium thionitrosyl, which is characterized by a wide array of spectroscopic methods (including the 15 N enriched isotopologue), and single crystal X-ray diffraction studies.…”