Fumika Sueyoshi, Kosei Yamauchi, Ken Sakai. “Concentration-dependent transition in the rate-determining step of hydrogen evolution driven by pyridinium-tethered mononuclear and dinuclear platinum photocatalysts.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15006300/v2

A mechanistic interpretation of calculated redox-species abundance changes was not retained

[PtCl₂(pBp)]²⁺, [Pt₂Cl₄(OpBp)]⁴⁺ and [Pt₂Cl₄(UpBp)]⁴⁺
Abstract-reported separation between two successive pBp²⁺-based one-electron reductions 290-320 mV
Abstract-reported comproportionation-constant range Kc = 1.0–3.2 × 10⁵
Estimated Cat²⁻ abundance based on the large comproportionation constants Minor component (e.g., 0.2 % of the total complex)
Luminescence, room temperature, solid and solution states Non-emissive
Luminescence spectra of [PtCl₂(pBp)](PF₆)₂, [Pt₂Cl₄(OpBp)](PF₆)₄, and [Pt₂Cl₄(UpBp)](PF₆)₄, frozen 4:4:1 (v/v/v) MeOH/EtOH/DMF glass contained in a quartz EPR tube, 77 K, excitation at 390 nm, qualitative observations Fundamentally consistent spectra with vibrational structure; dimer emission bands were slightly red-shifted; Stokes shifts were more than 100 nm; the luminescence was assignable to phosphorescence from the ³MX-LCT states
Emission-decay acquisition for [PtCl₂(pBp)](PF₆)₂, [Pt₂Cl₄(OpBp)](PF₆)₄, and [Pt₂Cl₄(UpBp)](PF₆)₄ in MED glass at 77 K Excitation at 374 nm; emission at 510, 514, and 519 nm, respectively
[PtCl₂(pBp)]²⁺ emission properties at 77 K: λₑₘ, nm; τₑₘ, µs; E₀₋₀, eV 510, 548; 7.3; 2.43
[Pt₂Cl₄(OpBp)]⁴⁺ emission properties at 77 K: λₑₘ, nm; τₑₘ, µs with fractional intensity f; τₐᵥₑ, µs; E₀₋₀, eV 514, 554; 1.9 (f = 0.059), 8.3 (f = 0.94); 6.9; 2.41
[Pt₂Cl₄(UpBp)]⁴⁺ emission properties at 77 K: λₑₘ, nm; τₑₘ, µs with fractional intensity f; τₐᵥₑ, µs; E₀₋₀, eV 519, 562; 1.4 (f = 0.049), 7.8 (f = 0.95); 6.3; 2.39
Emission-decay fit and lifetime definitions I = B₁ exp(−t/τ₁) + B₂ exp(−t/τ₂) + … + Bₙ exp(−t/τₙ) + A, where n is the number of exponents, τₙ is the lifetime, Bₙ is the pre-exponential factor, and A is a background offset; least-squares fitting used a single- or double-exponential function; fⱼ = Bⱼτⱼ / ∑ᵢⁿ Bᵢτᵢ; τₐᵥₑ = ∑ᵢⁿ fᵢτᵢ = ∑ᵢⁿ Bᵢτᵢ² / ∑ᵢⁿ Bᵢτᵢ
Cyclic and square-wave voltammetry, anhydrous DMF, cathodic polarization Two successive reversible waves from −0.4 to −1.1 V vs SCE and two irreversible reduction waves below ca. −1.5 V
Comproportionation constants defined in equations 1 and 2 [PtCl₂(pBp)]²⁺: Kc = 2.5 ×10⁵. [Pt₂Cl₄(OpBp)]⁴⁺: Kc = 7.9 ×10⁴. [Pt₂Cl₄(UpBp)]⁴⁺: Kc = 5.1 ×10⁵. Dimer values were estimated assuming that each mononuclear unit within the dimer undergoes redox processes independently, as if they were discrete monomers in solution
Main, pp. 1–3, 5, 7, 11–12; SI, pp. S9–S11
[PtCl₂(pBp)]²⁺, 0.05 mM in aqueous 5 vol% NMP solution
UV–Vis absorption spectroscopy Lowest-energy band centered at 391 nm; stronger absorption bands in the UV region at 327 and 341 nm
Main, pp. 4–5
[Pt₂Cl₄(OpBp)]⁴⁺ and [Pt₂Cl₄(UpBp)]⁴⁺, 0.025 mM in aqueous 5 vol% NMP solution
UV–Vis absorption spectroscopy Absorption features were essentially consistent with those observed for [PtCl₂(pBp)]²⁺; the UV bands for the dimers were both broadened and rather decreased in intensity
Main, pp. 4–5
Reduction-potential series in anhydrous DMF with 0.1 M TBAPF₆ under Ar, scan rate 100 mV/s; glassy-carbon working electrode (3 mmφ), platinum-wire counter electrode, and Ag/Ag⁺ reference electrode; potentials corrected using Fc/Fc⁺ = 0.45 V vs SCE as an internal standard
Methylviologen, MV²⁺, 0.5 mM, E₁; E₂; E₃; E₄, V vs SCE −0.47; −0.84; N.D.; N.D., respectively
[PtCl₂(pmBmp)]²⁺, 0.5 mM, E₁; E₂; E₃; E₄, V vs SCE −0.78; −1.28; −1.45; N.D., respectively
[PtCl₂(pBp)]²⁺, 0.5 mM, E₁; E₂; E₃; E₄, V vs SCE −0.52; −0.84; −1.63; −1.74
[Pt₂Cl₄(OpBp)]⁴⁺, 0.25 mM, E₁; E₂; E₃; E₄, V vs SCE −0.51; −0.80; −1.56; −1.69
[Pt₂Cl₄(UpBp)]⁴⁺, 0.25 mM, E₁; E₂; E₃; E₄, V vs SCE −0.53; −0.83; −1.60; −1.71
[PtCl₂(pmBmp)]²⁺, 0.5 mM, first reduction: cathodic peak potential, V; anodic peak potential, V; peak-to-peak separation, mV −0.823; −0.739; 84
[PtCl₂(pBp)]²⁺, 0.5 mM, first reduction: cathodic peak potential, V; anodic peak potential, V; peak-to-peak separation, mV; second reduction: cathodic peak potential, V; anodic peak potential, V; peak-to-peak separation, mV −0.560; −0.485; 75; −0.875; −0.795; 80
[Pt₂Cl₄(OpBp)]⁴⁺, 0.25 mM, first reduction: cathodic peak potential, V; anodic peak potential, V; peak-to-peak separation, mV; second reduction: cathodic peak potential, V; anodic peak potential, V; peak-to-peak separation, mV −0.570; −0.494; 76; −0.860; −0.791; 69
[Pt₂Cl₄(UpBp)]⁴⁺, 0.25 mM, first reduction: cathodic peak potential, V; anodic peak potential, V; peak-to-peak separation, mV; second reduction: cathodic peak potential, V; anodic peak potential, V; peak-to-peak separation, mV −0.585; −0.515; 70; −0.905; −0.800; 105
Reduction-potential reporting basis Potentials above −1.1 V were estimated using cyclic-voltammetry data; potentials in the more cathodic domain were determined using square-wave-voltammetry data
[Pt₂Cl₄(OpBp)]⁴⁺ and [Pt₂Cl₄(UpBp)]⁴⁺, electrochemical communication and electron count The two Pt(pBp) moieties showed negligible electrochemical communication; each displayed reduction step was assigned as a two-electron process
Main, pp. 6, 12; SI, pp. S12–S13
[PtCl₂(pBp)](PF₆)₂·3DMF crystal
Single-crystal X-ray diffraction, methylpyridinium-plane twist relative to the bpy plane 28.9-30.1°
Main, pp. 7–8; SI, p. S8
[OpBp](PF₆)₄·4DMF crystal
Single-crystal X-ray diffraction The two bpy units are widely separated
Main, p. 8; SI, p. S8
[PtCl₂(pBp)](PF₆)₂ (0.05 mM), [Pt₂Cl₄(OpBp)](PF₆)₄ (0.025 mM), and [Pt₂Cl₄(UpBp)](PF₆)₄ (0.025 mM) in aqueous acetate buffer (0.1 M, pH = 5.0) containing 5 vol% NMP, 15 vol% TFE, and EDTA (30 mM), under Ar atmosphere at 20 ºC; pH was measured after the addition of each solvent
In-situ dynamic light scattering before light irradiation, 660 nm diode laser, detection limit 0.6 nm in particle diameter Complete absence of heterogeneous species, evidenced by the lack of any significant exponential decay features in the autocorrelation functions
Main, pp. 10, 12; SI, pp. S15–S21
[PtCl₂(pBp)](PF₆)₂ (0.05 mM) and [Pt₂Cl₄(OpBp)](PF₆)₄ (0.025 mM) in aqueous acetate buffer (0.1 M, pH = 5.0) containing 5 vol% NMP, 15 vol% TFE, and EDTA (30 mM), under Ar atmosphere at 20 ºC; photolysis at 400 < λ < 800 nm and 300 mW cm⁻²; pH was measured after the addition of each solvent
In-situ dynamic light scattering during photoirradiation, 660 nm diode laser, detection limit 0.6 nm in particle diameter Any increase in light scattering intensity attributable to heterogeneous species, e.g., colloidal platinum particles, is negligible up to 5 h
Main, pp. 10, 12; SI, pp. S15–S19
[Pt₂Cl₄(UpBp)](PF₆)₄ (0.025 mM) in aqueous acetate buffer (0.1 M, pH = 5.0) containing 5 vol% NMP, 15 vol% TFE, and EDTA (30 mM), under Ar atmosphere at 20 ºC; photolysis at 400 < λ < 800 nm and 300 mW cm⁻²; the photolysis solution was exposed to air after 5 h of photoirradiation; pH was measured after the addition of each solvent
In-situ dynamic light scattering during photoirradiation and after exposure to air, 660 nm diode laser, detection limit 0.6 nm in particle diameter Light scattering intensity showed an immediate rise after only 1 min of light irradiation; DLS-active heterogeneous particles produced over 5 h of photoirradiation completely disappeared upon simple exposure to air
Main, pp. 10, 12; SI, pp. S15, S20–S21
[PtCl₂(pBp)]Cl₂ or [PtCl₂(pBp)](PF₆)₂, 0.05 mM, in aqueous acetate buffer (0.1 M, pH = 5.0) containing EDTA (30 mM) and NaCl (0.1 M); Ar atmosphere at 20 ºC; photolysis at 400 < λ < 800 nm; one photolysis solution was exposed to air after 1 h of photoirradiation
In-situ dynamic light scattering during photoirradiation and after exposure to air, 660 nm diode laser, detection limit 0.6 nm in particle diameter Heterogeneous dispersion immediately took place after 1 min of photoirradiation and was assignable to deposition of a 1-electron-reduced intermediate; the dispersion disappeared upon mere exposure to air
Main, pp. 10, 12; SI, pp. S22–S23
[PtCl₂(pBp)](PF₆)₂ (0.05 mM) in aqueous acetate buffer (0.1 M, pH = 5.0) containing EDTA (30 mM), 5 vol% NMP, and 15 vol% TFE, under Ar atmosphere at 20 ºC; photoirradiation at 400 < λ < 800 nm and 300 mW cm⁻²; pH was measured after the addition of each solvent
UV–Vis absorption spectroscopy, initial stage of photocatalysis Growth of bands at 450 and 745 nm was observed
Main, pp. 10–12
[PtCl₂(pBp)](PF₆)₂ (0.5 mM) in anhydrous DMF containing TBAPF₆ (0.1 M), under Ar atmosphere at 20 ºC; controlled-potential electrolysis at −0.6 V vs SCE for 0-14 min and −0.9 V vs SCE for 14-29 min; WE: Pt mesh, CE: Pt wire, RE: Ag/Ag⁺
UV–Vis–NIR spectroelectrochemistry at −0.6 V vs SCE, 80 mV more cathodic to E₁ Gradual growth of absorption bands at around 450 and 820 nm; the bands had the same origin as those evolving under the photocatalytic conditions; growth reached a plateau after 14 min
UV–Vis–NIR spectroelectrochemistry after switching from −0.6 to −0.9 V vs SCE, 60 mV more cathodic than E₂ Growth of the absorption bands was further promoted; the plateau absorbance reached at −0.9 V was nearly two times higher than at −0.6 V; Abs₅₀₀/Abs₈₂₀ remained roughly unchanged, whereas Abs₄₅₀/Abs₈₂₀ showed a noticeable increase
Main, pp. 10–11; SI, p. S14
[PtCl₂(pBp)]Cl₂ (0.1 mM) in aqueous acetate buffer solution (0.1 M, pH = 5.0), during controlled-potential electrolysis at −0.65 V vs SCE under Ar atmosphere; [Cat]ₜ = 0.1 mM
Calculated relative abundances at the electrode surface, assuming all catalyst molecules within the electroactive surface layer had undergone 1-electron reduction Cat: 0.2 %; Cat⁻: 99.6 %; Cat²⁻: 0.2 %
Main, p. 11; SI, p. S28
[OpBp](PF₆)₄·2H₂O
¹H NMR (600 MHz, DMSO-d₆), δ/ppm 5.71 (s, 8H), 7.68 (s, 8H), 8.21 (d, 8H, J = 7.6 Hz), 8.44 (dd, 4H, J = 8.4, 2.3 Hz), 8.59 (d, 4H, J = 9.2 Hz), 9.02 (d, 8H, J = 7.5 Hz), 9.18 (d, 4H, J = 2.2 Hz), 11.76 (s, 4H)
Elemental analysis for C₆₀H₄₈N₁₂O₄F₂₄P₄·2H₂O (1617.01), calcd; found, % C 44.57, H 3.24, N 10.39; C 44.59, H 3.48, N 10.19
ESI-TOF MS (acetonitrile, positive mode), m/z 250.05 ([OpBp]⁴⁺; calcd, 250.10), 645.04 ([OpBp⁴⁺ + 2PF₆⁻]²⁺; calcd, 645.16)
Main, p. 12; SI, pp. S2, S4
1-methyl-4-(5′-(pyridin-4-ylcarbamoyl)-[2,2′-bipyridine]-5-carboxamido)pyridin-1-ium iodide 4.5-hydrate
¹H NMR (400 MHz, DMSO-d₆), δ/ppm 4.21 (s, 3H), 7.81 (dd, 2H, J = 5.0, 1.9 Hz), 8.26 (d, 2H, J = 6.2 Hz), 8.54 (m, 3H), 8.58 (dd, 1H, J = 8.4, 2.3 Hz), 8.65 (d, 1H, J = 8.3 Hz), 8.68 (d, 1H, J = 8.3 Hz), 8.76 (d, 2H, J = 6.6 Hz), 9.28 (d, 1H, J = 2.4 Hz), 9.33 (d, 1H, J = 2.4 Hz), 10.91 (s, 1H), 11.83 (s, 1H)
Elemental analysis for C₂₃H₁₉N₆O₂I·4.5H₂O (619.42), calcd; found, % C 44.78, H 4.56, N 13.44; C 44.60, H 4.56, N 13.57
Main, p. 12
[UpBp](PF₆)₄·4.5H₂O
¹H NMR (600 MHz, DMSO-d₆), δ/ppm 4.23 (s, 6H), 5.76 (s, 4H), 7.58 (s, 4H), 8.30 (d, 4H, J = 7.4 Hz), 8.35 (d, 4H, J = 7.6 Hz), 8.59 (m, 4H), 8.69 (m, 4H), 8.80 (d, 4H, J = 7.6 Hz), 8.98 (d, 4H, J = 7.4 Hz), 9.33 (m, 4H), 11.81 (s, 2H), 11.90 (s, 2H)
Elemental analysis for C₅₄H₄₆N₁₂O₄F₂₄P₄·4.5H₂O (1587.96), calcd; found, % C 40.84, H 3.49, N 10.58; C 40.89, H 3.49, N 10.44
Main, pp. 12–13; SI, p. S2
[PtCl₂(pBp)](PF₆)₂·4.5H₂O
¹H NMR (600 MHz, CD₃CN), δ/ppm 4.18 (s, 6H), 8.23 (d, 4H, J = 7.3 Hz), 8.46 (m, 6H), 8.79 (dd, 2H, J = 8.4, 2.0 Hz), 10.16 (d, 2H, J = 2.1 Hz)
Elemental analysis for C₂₄H₂₂N₆O₂F₁₂P₂Cl₂Pt·4.5H₂O (1063.46), calcd; found, % C 27.11, H 2.94, N 7.69; C 27.03, H 2.73, N 7.69
ESI-TOF MS (acetonitrile, positive mode), m/z 345.98 ([PtCl₂(pBp)]²⁺; calcd, 346.04), 690.96 ({[PtCl₂(pBp)]²⁺ − H⁺}⁺; calcd, 691.07)
Main, p. 13; SI, pp. S3, S5
[PtCl₂(pBp)]Cl₂·2.5H₂O
Elemental analysis for C₂₄H₂₂N₆O₂Cl₄Pt·2.5H₂O (808.40), calcd; found, % C 35.66, H 3.37, N 10.40; C 35.56, H 3.12, N 10.17
ESI-TOF MS (acetonitrile/water = 1:1 v/v, positive mode), m/z 690.95 ({[PtCl₂(pBp)]²⁺ − H⁺}⁺; calcd, 691.07), 350.52 ({[PtCl₂(pBp)]²⁺ − 2Cl⁻ − 2H⁺ + 2CH₃CN}²⁺; calcd, 350.59)
Main, p. 13
[Pt₂Cl₄(OpBp)](PF₆)₄·5H₂O
¹H NMR (400 MHz, DMSO-d₆), δ/ppm 5.73 (s, 8H), 7.68 (s, 8H), 8.20 (d, 8H, J = 7.6 Hz), 8.81 (d, 4H, J = 8.4 Hz), 8.88 (d, 4H, J = 8.2 Hz), 9.03 (d, 8H, J = 7.6 Hz), 9.86 (d, 4H, J = 2.1 Hz), 12.03 (s, 4H)
Elemental analysis for C₆₀H₄₈N₁₂O₄F₂₄P₄Cl₄Pt₂·5H₂O (2203.02), calcd; found, % C 32.71, H 2.62, N 7.66; C 32.56, H 2.65, N 7.63
ESI-TOF MS (acetonitrile, positive mode), m/z 382.95 ([Pt₂Cl₄(OpBp)]⁴⁺; calcd, 383.05), 764.89 ({[Pt₂Cl₄(OpBp)]⁴⁺ − 2H⁺}²⁺; calcd, 765.09)
Main, p. 13; SI, pp. S3, S5
[Pt₂Cl₄(UpBp)](PF₆)₄·4H₂O
¹H NMR (400 MHz, DMSO-d₆), δ/ppm 4.24 (s, 6H), 5.77 (s, 4H), 7.59 (s, 4H), 8.27 (d, 4H, J = 7.2 Hz), 8.32 (d, 4H, J = 6.4 Hz), 8.82 (d, 4H, J = 6.7 Hz), 8.90-9.01 (m, 12H), 10.02 (d, 2H, J = 2.2 Hz), 12.06 (s, 2H), 12.16 (s, 2H)
Elemental analysis for C₅₄H₄₆N₁₂O₄F₂₄P₄Cl₄Pt₂·4H₂O (2110.92), calcd; found, % C 30.73, H 2.58, N 7.96; C 30.77, H 2.77, N 7.83
ESI-TOF MS (acetonitrile, positive mode), m/z 874.39 ({[Pt₂Cl₄(UpBp)]⁴⁺ + 2PF₆⁻}²⁺; calcd, 874.55), 485.61 ({[Pt₂Cl₄(UpBp)]⁴⁺ − H⁺}³⁺; calcd, 485.72)
Main, p. 13; SI, pp. S4, S6
Single-crystal X-ray diffraction data for [OpBp](PF₆)₄·4DMF and [PtCl₂(pBp)](PF₆)₂·3DMF
Formula [OpBp](PF₆)₄·4DMF: C₇₂H₇₆F₂₄N₁₆O₈P₄; [PtCl₂(pBp)](PF₆)₂·3DMF: C₃₃H₄₃Cl₂F₁₂N₉O₅P₂Pt
Formula weight [OpBp](PF₆)₄·4DMF: 1873.36; [PtCl₂(pBp)](PF₆)₂·3DMF: 1201.69
Color, habit [OpBp](PF₆)₄·4DMF: colorless, prisms; [PtCl₂(pBp)](PF₆)₂·3DMF: orange, prisms
Crystal size, mm [OpBp](PF₆)₄·4DMF: 0.02×0.02×0.01; [PtCl₂(pBp)](PF₆)₂·3DMF: 0.28×0.10×0.02
Crystal system [OpBp](PF₆)₄·4DMF: Monoclinic; [PtCl₂(pBp)](PF₆)₂·3DMF: Triclinic
Space group [OpBp](PF₆)₄·4DMF: P2₁/c (No. 14); [PtCl₂(pBp)](PF₆)₂·3DMF: P1̅ (No. 2)
a, Å [OpBp](PF₆)₄·4DMF: 8.6508(3); [PtCl₂(pBp)](PF₆)₂·3DMF: 10.5961(2)
b, Å [OpBp](PF₆)₄·4DMF: 17.2978(4); [PtCl₂(pBp)](PF₆)₂·3DMF: 12.7801(3)
c, Å [OpBp](PF₆)₄·4DMF: 26.8004(6); [PtCl₂(pBp)](PF₆)₂·3DMF: 18.3569(4)
α, deg [OpBp](PF₆)₄·4DMF: 90; [PtCl₂(pBp)](PF₆)₂·3DMF: 74.742(2)
β, deg [OpBp](PF₆)₄·4DMF: 98.474(2); [PtCl₂(pBp)](PF₆)₂·3DMF: 76.615(2)
γ, deg [OpBp](PF₆)₄·4DMF: 90; [PtCl₂(pBp)](PF₆)₂·3DMF: 69.239(2)
V, ų [OpBp](PF₆)₄·4DMF: 3966.62(19); [PtCl₂(pBp)](PF₆)₂·3DMF: 2216.05(9)
Z [OpBp](PF₆)₄·4DMF: 2; [PtCl₂(pBp)](PF₆)₂·3DMF: 2
F(000) [OpBp](PF₆)₄·4DMF: 1920; [PtCl₂(pBp)](PF₆)₂·3DMF: 1188
Calculated density, g/cm³ [OpBp](PF₆)₄·4DMF: 1.568; [PtCl₂(pBp)](PF₆)₂·3DMF: 1.801
μ, mm⁻¹ [OpBp](PF₆)₄·4DMF: 1.976; [PtCl₂(pBp)](PF₆)₂·3DMF: 3.460
Transmission coefficient [OpBp](PF₆)₄·4DMF: 0.57603 - 1.00000; [PtCl₂(pBp)](PF₆)₂·3DMF: 0.48266 - 1.00000
Temperature, K [OpBp](PF₆)₄·4DMF: 100(2); [PtCl₂(pBp)](PF₆)₂·3DMF: 100(2)
Radiation, Å [OpBp](PF₆)₄·4DMF: 1.54184; [PtCl₂(pBp)](PF₆)₂·3DMF: 0.71073
Theta range, deg [OpBp](PF₆)₄·4DMF: 3.051 < theta < 66.601; [PtCl₂(pBp)](PF₆)₂·3DMF: 2.534 < theta < 25.026
Index ranges [OpBp](PF₆)₄·4DMF: -9<h<10, -13<k<20, -31<l<31; [PtCl₂(pBp)](PF₆)₂·3DMF: -12<h<12, -15<k<15, -21<l<21
Reflections measured [OpBp](PF₆)₄·4DMF: 27656; [PtCl₂(pBp)](PF₆)₂·3DMF: 29236
Unique reflections [OpBp](PF₆)₄·4DMF: 6986; [PtCl₂(pBp)](PF₆)₂·3DMF: 7822
Rᵢₙₜ [OpBp](PF₆)₄·4DMF: 0.0711; [PtCl₂(pBp)](PF₆)₂·3DMF: 0.0503
Data/restraints/parameters [OpBp](PF₆)₄·4DMF: 6986/0/563; [PtCl₂(pBp)](PF₆)₂·3DMF: 7822/0/585
R₁ [OpBp](PF₆)₄·4DMF: 0.0692; [PtCl₂(pBp)](PF₆)₂·3DMF: 0.0306
wR₂ [OpBp](PF₆)₄·4DMF: 0.1992; [PtCl₂(pBp)](PF₆)₂·3DMF: 0.0762
Weighting scheme [OpBp](PF₆)₄·4DMF: w=1/[σ²(Fₒ²)+(0.1176P)²+3.4713P], where P=(Fₒ²+2F(calculated)²)/3; [PtCl₂(pBp)](PF₆)₂·3DMF: w=1/[σ²(Fₒ²)+(0.0372P)²+1.0688P], where P=(Fₒ²+2F(calculated)²)/3
GOF [OpBp](PF₆)₄·4DMF: 1.052; [PtCl₂(pBp)](PF₆)₂·3DMF: 1.077
Maximum/mean shift/esd [OpBp](PF₆)₄·4DMF: 0.000/0.000; [PtCl₂(pBp)](PF₆)₂·3DMF: 0.003/0.000
Maximum/minimum difference peaks [OpBp](PF₆)₄·4DMF: 0.712/-0.371; [PtCl₂(pBp)](PF₆)₂·3DMF: 2.796/-0.521