Madeline N. Riffel, Oluwafemi O. Ishola, Allen G. Oliver, Emily Y. Tsui. “Proton-induced perthionitrite-mediated zinc thiolate persulfidation.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007547/v1

The approximate SSNO⁻ reaction-yield claim was not retained

Compound
Identifier 1-ONO
¹H NMR (600 MHz, DMSO-d₆) δ 8.29 (t, J = 7.8 Hz, 1H), 8.10 (d, J = 7.6 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 5.48 (d, J = 6.8 Hz, 1H, NH), 3.65 (m, 1H), 3.60 (m, 1H), 3.52 (m, 1H), 3.07 (m, 2H), 2.91 (m, 1H), 2.62 (m, 2H), 2.46 (s, 3H), 1.87 (s, 3H) ppm
¹³C NMR (100 MHz, DMSO-d₆) δ 161.7, 145.9, 142.8, 125.6, 122.2, 78.1, 53.0, 49.6, 35.5, 29.5, 28.0, 15.2 ppm
¹H NMR spectrum annotation H2O and MeCN were present
FTIR (KBr pellet, cm⁻¹) ν = 1369 (N=O, m), 1063 (N–O, m)
Elemental analysis, calculated for C₁₃H₁₈N₄O₂S₂Zn C, 39.85; H, 4.63; N, 14.30
Elemental analysis, found C, 39.80; H, 4.68; N, 14.14
SCXRD, empirical formula; formula weight; temperature C₂₆H₃₆N₈O₄S₄Zn₂; 783.61; 120 K
SCXRD, crystal system; space group Triclinic; P-1
SCXRD, unit-cell dimensions a = 9.1127(8) Å, b = 9.7271(9) Å, c = 10.1213(9) Å; α = 61.7810(10)°, β = 83.3700(10)°, γ = 84.655(2)°
SCXRD, volume; Z 784.48(12) ų; 1
SCXRD, calculated density; absorption coefficient; F(000) 1.659 g cm⁻³; 1.843 mm⁻¹; 404
SCXRD, crystal size; radiation 0.255 × 0.207 × 0.126 mm³; Mo Kα, λ = 0.71073 Å
SCXRD, 2θ collection range; index ranges 4.504–63.28°; −13 ≤ h ≤ 12, −14 ≤ k ≤ 13, −14 ≤ l ≤ 14
SCXRD, reflections collected; independent reflections 13918; 4823 [Rint = 0.0117, Rsigma = 0.0131]
SCXRD, data/restraints/parameters; goodness-of-fit on F² 4823/0/213; 1.055
SCXRD, final R indexes [I ≥ 2σ(I)] R1 = 0.0213, wR2 = 0.0540
SCXRD, final R indexes [all data] R1 = 0.0229, wR2 = 0.0548
SCXRD, largest difference peak/hole 0.95/−0.30 e Å⁻³
SI, pp. S3–S4, S23–S24
¹⁵N-labelled form of the product designated 1-ONO
Identifier 1-O15NO
¹⁵N NMR {¹H} (50.7 MHz, DMSO-d₆), external MeNO2 reference δ 222.7 ppm
SI, pp. S2–S3
Monometallic zinc perthiolate complex bearing a perthionitrite ligand
Identifier 2-SSNO
FTIR (KBr pellet), Main ν(S–N) 654 cm⁻¹; the N–O stretch was obscured by other ligand-derived vibrations
FTIR (KBr pellet), SI ν(S–N) 656 cm⁻¹ (m)
UV–vis (MeCN) λmax 416 nm (ε = 1800 M⁻¹ cm⁻¹)
ESI–MS (DMSO/MeCN, direct injection), Main m/z 471.9076 [2-SSNO+H]+, 439.9364 [1-SSNO+H]+, 375.9912 [2]+, 344.0200 [1]+
ESI–MS (DMSO/MeCN, direct injection), SI m/z [2]+ calcd for C₁₃H₁₈N₃S₃ 375.9954, found 375.9912; [2 − S]+ calcd for C₁₃H₁₈N₃S₂ 344.0234, found 344.0200; [2 + S]+ calcd for C₁₃H₁₈N₃S₄ 407.9675, found 407.9629
Elemental analysis, calculated for C₁₃H₁₈ON₄S₅Zn C, 33.08; H, 3.84; N, 11.87
Elemental analysis, found C, 34.09; H, 4.01; N, 11.63
Stability of isolated crystals under inert atmosphere Stable over several days
SCXRD, structure Monometallic zinc perthiolate complex with an SSNO− ligand bound in a κ1 fashion at the terminal S atom; two independent molecules in the asymmetric unit
SCXRD, disorder The SSNO ligands were disordered over two sites with occupancy ratios 0.63:0.37 and 0.55:0.45, preventing comparison of precise bond distances and angles; C24 was disordered over two sites with an occupancy ratio of 0.62:0.38
SCXRD, empirical formula; formula weight; temperature C₁₃H₁₈N₄OS₅Zn; 471.98; 120 K
SCXRD, crystal system; space group Monoclinic; P21/n
SCXRD, unit-cell dimensions a = 17.4059(7) Å, b = 11.5678(6) Å, c = 19.7498(9) Å; α = 90°, β = 109.939(2)°, γ = 90°
SCXRD, volume; Z 3738.2(3) ų; 8
SCXRD, calculated density; absorption coefficient; F(000) 1.677 g cm⁻³; 7.13 mm⁻¹; 1936
SCXRD, crystal size; radiation 0.242 × 0.073 × 0.028 mm³; Cu Kα, λ = 1.54178 Å
SCXRD, 2θ collection range; index ranges 5.856–150.122°; −19 ≤ h ≤ 21, −14 ≤ k ≤ 14, −24 ≤ l ≤ 24
SCXRD, reflections collected; independent reflections 156664; 7680 [Rint = 0.0777, Rsigma = 0.0295]
SCXRD, data/restraints/parameters; goodness-of-fit on F² 7680/167/503; 1.046
SCXRD, final R indexes [I ≥ 2σ(I)] R1 = 0.0928, wR2 = 0.2743
SCXRD, final R indexes [all data] R1 = 0.1026, wR2 = 0.2866
SCXRD, largest difference peak/hole 1.36/−1.14 e Å⁻³
Main, pp. 3–5; SI, pp. S2–S4, S23–S24
¹⁵N-labelled monometallic zinc perthiolate complex bearing a perthionitrite ligand
Identifier 2-SS15NO
¹⁵N NMR {¹H} (50.7 MHz, DMSO-d₆), external MeNO2 reference, Main δ 336 ppm vs. MeNO2
¹⁵N NMR {¹H} (50.7 MHz, DMSO-d₆), external MeNO2 reference, SI δ 337 ppm
FTIR (KBr pellet) ν(S–¹⁵N) approximately 638 cm⁻¹
Main, pp. 3–4; SI, pp. S2–S3
Thiolate-supported zinc thionitrite complex
Identifier 1-SNO
¹H NMR (400 MHz, d₆-DMSO) δ 8.31 (t, J = 7.6 Hz, 1H), 8.12 (d, J = 7.6 Hz, 1H), 7.97 (d, J = 7.6 Hz, 1H), 5.57 (s, 1H) 3.71 (m, 1H), 3.55 (m, 2H), 3.08 (m, 2H), 2.941 (m, 1H), 2.72 (m, 2H), 2.47 (s, 3H), 1.82 (s, 3H) ppm
Solution stability at room temperature Approximately 20 % decomposition in 1 h
FTIR (KBr pellet, cm⁻¹) ν(NO) 1425, ν(SN) 679
UV–vis (MeCN), Main λmax 343 nm (ε = 2700 M⁻¹ cm⁻¹)
UV–vis (MeCN), SI λmax 340 nm (ε = 2700 M⁻¹ cm⁻¹)
Elemental analysis, calculated for C₁₃H₁₈N₄OS₃Zn C, 38.28; H, 4.45; N, 13.74
Elemental analysis, found C, 38.49; H, 4.61; N, 13.73
SCXRD, structure The SNO− ligand coordinates at Zn through the S atom and adopts an anti conformation
SCXRD, empirical formula; formula weight; temperature C₁₃H₁₈N₄OS₃Zn; 407.86; 120 K
SCXRD, crystal system; space group Triclinic; P-1
SCXRD, unit-cell dimensions a = 7.5560(3) Å, b = 10.7088(4) Å, c = 12.0156(5) Å; α = 103.5916(13)°, β = 104.0695(13)°, γ = 109.4482(12)°
SCXRD, volume; Z 834.54(6) ų; 2
SCXRD, calculated density; absorption coefficient; F(000) 1.623 g cm⁻³; 1.852 mm⁻¹; 420.0
SCXRD, crystal size; radiation 0.244 × 0.217 × 0.176 mm³; Mo Kα, λ = 0.71073 Å
SCXRD, 2θ collection range; index ranges 4.298–56.57°; −10 ≤ h ≤ 10, −14 ≤ k ≤ 14, −15 ≤ l ≤ 15
SCXRD, reflections collected; independent reflections 32030; 4124 [Rint = 0.0238, Rsigma = 0.0134]
SCXRD, data/restraints/parameters; goodness-of-fit on F² 4124/0/201; 1.078
SCXRD, final R indexes [I ≥ 2σ(I)] R1 = 0.0225, wR2 = 0.0636
SCXRD, final R indexes [all data] R1 = 0.0230, wR2 = 0.0640
SCXRD, largest difference peak/hole 0.75/−0.36 e Å⁻³
Main, pp. 3–4; SI, pp. S4, S23–S24
¹⁵N-labelled thiolate-supported zinc thionitrite complex
Identifier 1-S15NO
¹⁵N NMR {¹H} (52 MHz, DMSO-d₆), external MeNO2 reference δ 505 ppm
¹⁵N NMR time course SS15NO− formed during solution decomposition and increased with time
SI, pp. S2, S4, S7
Disulfide-bridged, metal-free macrocycle grown from the 2-SSNO synthesis supernatant
Identifier 4
SCXRD, empirical formula; formula weight; temperature C₁₃H₂₀N₃S₂; 282.44; 120 K
SCXRD, crystal system; space group Triclinic; P-1
SCXRD, unit-cell dimensions a = 8.0678(7) Å, b = 8.9594(7) Å, c = 9.8017(7) Å; α = 77.171(2)°, β = 84.479(2)°, γ = 88.929(3)°
SCXRD, volume; Z 687.60(9) ų; 2
SCXRD, calculated density; absorption coefficient; F(000) 1.364 g cm⁻³; 0.374 mm⁻¹; 302
SCXRD, crystal size; radiation 0.176 × 0.129 × 0.103 mm³; Mo Kα, λ = 0.71073 Å
SCXRD, 2θ collection range; index ranges 4.662–56.564°; −10 ≤ h ≤ 10, −11 ≤ k ≤ 11, −13 ≤ l ≤ 10
SCXRD, reflections collected; independent reflections 21269; 3399 [Rint = 0.0286, Rsigma = 0.0195]
SCXRD, data/restraints/parameters; goodness-of-fit on F² 3399/0/165; 1.055
SCXRD, final R indexes [I ≥ 2σ(I)] R1 = 0.0276, wR2 = 0.0778
SCXRD, final R indexes [all data] R1 = 0.0287, wR2 = 0.0787
SCXRD, largest difference peak/hole 0.40/−0.32 e Å⁻³
Main, pp. 4–5; SI, pp. S23–S25
DMSO-d₆ solution prepared from crystals of the monometallic zinc perthiolate complex bearing a perthionitrite ligand
Identifier 2-SSNO
Composition 2-SSNO was in exchange with 1-SSNO and “S⁰,” presumably in the form of S8
¹H NMR (500 MHz, DMSO-d₆), resonances assigned to 2-SSNO δ 8.39 (t, J = 7.9 Hz, 1H), 8.28 (d, J = 7.7 Hz, 1H), 8.10 (d, J = 8.0 Hz, 1H), 5.42 (d, J = 8.9 Hz, 1H, NH), 4.35 (d, J = 13.8 Hz, 1H), 4.06 (t, J = 13.8 Hz, 1H), 3.65 (m, 2H), 3.50 (m, 1H), 3.41 (m, 1 H), 2.72–2.59 (m, 2H), 1.82 (s, 3H) ppm
¹H NMR (500 MHz, DMSO-d₆), resonances assigned to 1-SSNO δ 8.32 (t, J = 7.6 Hz, 1H), 8.12 (d, J = 7.6 Hz, 1H), 8.00 (d, J = 7.6 Hz, 1H), 5.63 (d, J = 12 Hz, 1H, NH), 3.14–3.04 (m, 5H), 2.97–2.87 (m, 3H), 2.46 (s, 3H), 1.93 (s, 3H) ppm
¹H NMR spectrum annotation H2O, MeCN, and a decomposition product were present
Stability at room temperature New products with downfield-shifted ligand ¹H NMR resonances and H2O formed over one day; t1/2 was approximately 7 h, and the SSNO− absorption band bleached
TPPCo trapping, NO quantification after 19 h 0.91 equivalents
Main, pp. 4–5; SI, pp. S3–S4, S6
Atmosphere above a DMSO reaction mixture of [1]₃[OTf]₃ and [PNP][SSNO], exposed to TPPCo in CDCl₃
NO quantification after 19 h by ¹H NMR (CDCl₃, d1 = 30 s) 0.91 equivalents, from integrations of TPPCo and TPPCo(NO)
SI, pp. S17–S18
DMSO-d₆ solution prepared from crystals of the monometallic zinc perthiolate complex after addition of PPh3
Identifier 2-SSNO
¹H NMR Resonances assigned to 2-SSNO at δ 8.4, 8.25, and 8.08 ppm decreased, and resonances assigned to 1-SSNO at δ 8.3, 8.1, and 7.97 ppm increased
¹H NMR spectrum annotation Resonances assigned to 3 were indicated
³¹P NMR One equivalent of SPPh3 was formed within 10 min, even with excess PPh3
Main, p. 4; SI, p. S13
DMSO-d₆ solution prepared from crystals of the monometallic zinc perthiolate complex after addition of S8
Identifier 2-SSNO
¹H NMR, one S-atom equivalent The species assigned to 2-SSNO was enriched
Main, p. 4; SI, p. S13
DMSO-d₆ solution of ¹⁵N-labelled monometallic zinc perthiolate complex with PPh3
Identifier 2-SS15NO
¹⁵N NMR {¹H}, external MeNO2 reference A single resonance at δ 336 ppm
SNO− by ¹⁵N NMR within 10 min Not observed; reference δ 529 ppm
Main, p. 4; SI, pp. S2, S12
MeCN solution of the monometallic zinc perthiolate complex with PPh3
Identifier 2-SSNO
UV–vis (22 °C), 1.6 equivalents PPh3 No SNO− was observed within 10 min; λmax approximately 340 nm
Main, p. 4; SI, p. S12
DMSO/MeCN solution of the monometallic zinc perthiolate complex with PPh3
Identifier 2-SSNO
ESI–MS, direct injection Primarily the signal corresponding to [1]+
Main, p. 4; SI, p. S11
DMSO-d₆ solution of the thiolate-supported zinc thionitrite complex after addition of S8
Identifier 1-SNO
¹H NMR, 1/8 and 3/8 equivalents S8 The authors assigned formation first of 1-SSNO, followed by 2-SSNO upon addition of more S8; some decomposition product 3 was also present
Main, p. 4; SI, p. S13
MeCN solution of the thiolate-supported zinc thionitrite complex after addition of S8
Identifier 1-SNO
UV–vis, 0.8 mM 1-SNO and one S-atom equivalent A new band with λmax approximately 420 nm, assigned by the authors to 1-SSNO
SI, p. S14
Reaction of the product designated 1-NO2 in the Main with S8
¹H NMR (DMSO-d₆) Downfield-shifted products were observed
SNO− and SSNO− Neither was observable
Main, p. 5
Reaction of the product designated 1-ONO in the SI with two equivalents of sulfur
NO quantification after 19 h by ¹H NMR (CDCl₃, d1 = 30 s) 0.55 equivalents, from integrations of TPPCo and TPPCo(NO)
SI, p. S17
DMSO and MeCN solutions of the thiolate-supported zinc thionitrite complex at room temperature
Identifier 1-SNO
Stability t1/2 approximately 20 min; ¹H NMR showed similar downfield-shifted peaks as proposed complex 3
Main, p. 5
Thermal decomposition of a DMSO solution of the thiolate-supported zinc thionitrite complex
Identifier 1-SNO
NO quantification after 19 h Main: ca. 0.8 equivalents; SI ¹H NMR (CDCl₃, d1 = 30 s): ca. 0.82 equivalents, from integrations of TPPCo and TPPCo(NO)
Main, p. 5; SI, pp. S17, S19
MeCN solution of the thiolate-supported zinc thionitrite complex at room temperature
Identifier 1-SNO
UV–vis 1-SNO 0.3 mM; spectra at 100 and 235 min showed formation and decay of SSNO−; absorbance at 337 nm for 1-SNO and 440 nm for SSNO− was plotted against time
SI, p. S15
MeCN solution of [PNP][SNO] after addition of the self-assembled trimeric zinc cluster
Zinc-complex identifier [1]3[OTf]3
UV–vis [PNP][SNO] 0.4 mM and [1]3[OTf]3 0.13 mM; the band at 335 nm decreased and a band at 441 nm assigned to free SSNO− grew; spectra were measured immediately and after 60 min
Main, pp. 5–6
Self-assembled trimeric zinc cluster treated with [Bu4N]2[S6]
Identifier [1]3[OTf]3
Powder XRD The authors assigned formation of ZnS
Main, p. 5
Monomeric zinc DMSO complex treated with different amine bases in DMSO-d₆
Identifier [1-DMSO][OTf]
¹H NMR Resonances assigned by the authors to proposed dithiolate complex 3 were observed
Main, p. 5; SI, p. S14
Material designated 1-Cl after addition of S8
¹H NMR Resonances assigned by the authors to proposed dithiolate complex 3 were observed
Main, p. 5
Supernatant from the synthesis of the monometallic zinc perthiolate complex bearing a perthionitrite ligand
¹H NMR (DMSO-d₆) [PNP]⁺ and downfield aromatic peaks assigned by the authors to proposed dithiolate complex 3 were observed
SI, p. S15
[PNP][SSNO] treated with [Et4N][tolS]
¹H NMR (DMSO-d₆), one equivalent [PNP][SSNO] No S⁰ transfer from SSNO− to tolS−; no resonances corresponding to tolSS− or higher-order polysulfanide anions were observed; trace H2O was present
UV–vis (MeCN), 0.0032 M [PNP][SSNO] No conversion of SSNO− to SNO− over 1 h at room temperature; the 440 nm band bleached by less than 5 %
Main, p. 6; SI, pp. S20–S21
[PNP][SSNO] treated with [Et4N][BuS]
¹H NMR (DMSO-d₆), one equivalent [PNP][SSNO] No S⁰ transfer from SSNO− to BuS−
UV–vis (MeCN), 0.0034 M [PNP][SSNO] No conversion of SSNO− to SNO− over 5 h at room temperature
Main, p. 6; SI, pp. S20–S21
[PNP][SSNO] treated with BuSH
UV–vis (MeCN), 0.0047 M [PNP][SSNO], one equivalent BuSH Consumption of SSNO− and growth of a band at 330 nm consistent with BuSS− over 3 h at room temperature