Abstract:Osmiumpentachlorid reagiert mit Trithiazylchlorid, (NSCl)3, unter Bildung des Thiazylchloridkomplexes [OsCl4(NSCl)2], aus dem mit Tetraphenylarsoniumchlorid in Dichlormethanlösung der Thionitrosyl‐Komplex AsPh4[OsCl4(NS)2Cl] entsteht. Mit Galliumtrichlorid läßt sich hieraus der ungeladene Thionitrosylkomplex [OsCl4(NS)2] herstellen. Die IR‐Spektren der neuen Komplexe werden mitgeteilt und zugeordnet. Die Kristallstruktur von AsPh4[OsCl4(NS)2Cl] wurde mit Hilfe von Röntgenbeugungsdaten ermittelt und bis zu eine… Show more
“…The multiple bond character of the Os−N bond is in agreement with the short Os−N bond distances. The N−S bond lengths of 1.489(15) and 1.493(8) Å for 3c and 4 and are comparable to bond distances in other thionitrosyl complexes. 5e,, The N−S bond lengths are also consistent with largely NS + character by comparison with the NS + cation in which the N−S bond length is 1.495 Å . The Os−N−S bond angle is almost linear at 179.3(9)° in [Os II (tpm)(Cl) 2 (NS)] + and at 166.9(9)° in Os II (Tp)(Cl) 2 (NS).…”
Section: Discussionsupporting
confidence: 56%
“…Low-intensity bands for 3b and 4 appear in the region 540−420 cm -1 which shift ∼15 cm -1 in 15 N-labeled complexes. A related series of bands appear at 495, 454, and 221 cm -1 for [Os(NS)(NSCl)(Cl) 4 ] - which have been assigned to the normal modes ν s (Os−N), ν as (Os−N), and δ(Os−NS) …”
Section: Discussionmentioning
confidence: 99%
“…A related series of bands appear at 495, 454, and 221 cm -1 for [Os(NS)(NSCl)(Cl) 4 ] -which have been assigned to the normal modes ν s (Os-N), ν as (Os-N), and δ (Os-NS). 26 As shown in Figure 4, two bands of low absorptivity appear in the visible for both 3b and 4. In a molecular orbital scheme, with the Os-NS bond axis defined as z, dπ-π*(NS) mixing is dominated by d xz and d yz with the d xy (in-plane) orbital orthogonal to the dominant interaction.…”
Reaction between [Os(VI)(tpm)(Cl)(2)(N)](PF(6)) (tpm = tris(1-pyrazolyl)methane) (1) or Os(VI)(Tp)(Cl)(2)(N) (Tp = hydrotris(1-pyrazolyl)borate anion) (2) and CS(2) + N(3)(-) in acetone gives the corresponding thionitrosyl complexes, (-)SCN, and N(2). There is an extensive reactivity chemistry of the thionitrosyl group in [Os(II)(tpm)(Cl)(2)(NS)](PF(6)) (3b). Reaction between 3b and PPh(3) occurs with S-atom transfer to give [Os(IV)(tpm)(Cl)(2)(NPPh(3))](+) and S=PPh(3). 3b undergoes chemical or electrochemical reduction to give the corresponding Os(II) ammine complex and H(2)S. O-atom transfer from O=NMe(3) to 3b occurs to give Os(III)(tpm)(Cl)(2)(NSO). Competitive NO(+)/NS(+) exchange and S(2)(-) transfer occur in the reaction between [Os(II)(tpm)(Cl)(2)(NS)](BF(4)) (3c) and NO(+) to give a mixture of [Os(VI)(tpm)(Cl)(2)(N)](+) and [Os(II)(tpm)(Cl)(2)(NO)](+).
“…The multiple bond character of the Os−N bond is in agreement with the short Os−N bond distances. The N−S bond lengths of 1.489(15) and 1.493(8) Å for 3c and 4 and are comparable to bond distances in other thionitrosyl complexes. 5e,, The N−S bond lengths are also consistent with largely NS + character by comparison with the NS + cation in which the N−S bond length is 1.495 Å . The Os−N−S bond angle is almost linear at 179.3(9)° in [Os II (tpm)(Cl) 2 (NS)] + and at 166.9(9)° in Os II (Tp)(Cl) 2 (NS).…”
Section: Discussionsupporting
confidence: 56%
“…Low-intensity bands for 3b and 4 appear in the region 540−420 cm -1 which shift ∼15 cm -1 in 15 N-labeled complexes. A related series of bands appear at 495, 454, and 221 cm -1 for [Os(NS)(NSCl)(Cl) 4 ] - which have been assigned to the normal modes ν s (Os−N), ν as (Os−N), and δ(Os−NS) …”
Section: Discussionmentioning
confidence: 99%
“…A related series of bands appear at 495, 454, and 221 cm -1 for [Os(NS)(NSCl)(Cl) 4 ] -which have been assigned to the normal modes ν s (Os-N), ν as (Os-N), and δ (Os-NS). 26 As shown in Figure 4, two bands of low absorptivity appear in the visible for both 3b and 4. In a molecular orbital scheme, with the Os-NS bond axis defined as z, dπ-π*(NS) mixing is dominated by d xz and d yz with the d xy (in-plane) orbital orthogonal to the dominant interaction.…”
Reaction between [Os(VI)(tpm)(Cl)(2)(N)](PF(6)) (tpm = tris(1-pyrazolyl)methane) (1) or Os(VI)(Tp)(Cl)(2)(N) (Tp = hydrotris(1-pyrazolyl)borate anion) (2) and CS(2) + N(3)(-) in acetone gives the corresponding thionitrosyl complexes, (-)SCN, and N(2). There is an extensive reactivity chemistry of the thionitrosyl group in [Os(II)(tpm)(Cl)(2)(NS)](PF(6)) (3b). Reaction between 3b and PPh(3) occurs with S-atom transfer to give [Os(IV)(tpm)(Cl)(2)(NPPh(3))](+) and S=PPh(3). 3b undergoes chemical or electrochemical reduction to give the corresponding Os(II) ammine complex and H(2)S. O-atom transfer from O=NMe(3) to 3b occurs to give Os(III)(tpm)(Cl)(2)(NSO). Competitive NO(+)/NS(+) exchange and S(2)(-) transfer occur in the reaction between [Os(II)(tpm)(Cl)(2)(NS)](BF(4)) (3c) and NO(+) to give a mixture of [Os(VI)(tpm)(Cl)(2)(N)](+) and [Os(II)(tpm)(Cl)(2)(NO)](+).
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).
“…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.…”
Addition of elemental sulfur to the vanadium nitride [(nacnac)V≡N(OAr)] forms the first thionitrosyl complex of vanadium, [(nacnac)V(NS)(OAr)]. Single crystal X-Ray diffraction studies and DFT calculations reveal an almost linear thionitrosyl ligand resulting from an extended π-resonance across the VNS moiety.
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