J. Serb. Chem. Soc. 80 (3) S67 S73 (2015) Supplementary material

Μέγεθος: px

Εμφάνιση ξεκινά από τη σελίδα:

Download "J. Serb. Chem. Soc. 80 (3) S67 S73 (2015) Supplementary material"

Ευφήμιος Κουβέλης
5 χρόνια πριν
Προβολές:

the trans-influence of halogenido ligands IVANA DJORDJEVIĆ 1, SONJA GRUBIŠIĆ 1 *, MILOŠ MILČIĆ 2 and SVETOZAR NIKETIĆ 1 1 Center for Chemistry, ICTM, University of Belgrade, Njegoševa 12, 11001

1 J. Serb. Chem. Soc. 80 (3) S67 S73 (2015) Supplementary material SUPPLEMENTARY MATERIAL TO Derivation of a new set of force field parameters for ammine complexes of chromium(iii) containing halogeno ligands: modeling of the trans-influence of halogenido ligands IVANA DJORDJEVIĆ 1, SONJA GRUBIŠIĆ 1 *, MILOŠ MILČIĆ 2 and SVETOZAR NIKETIĆ 1 1 Center for Chemistry, ICTM, University of Belgrade, Njegoševa 12, Belgrade, Serbia and 2 Faculty of Chemistry, University of Belgrade, Studentski trg 16, Belgrade, Serbia J. Serb. Chem. Soc. 80 (3) (2015) TABLE S-I. Additional VOFF parameters for [Cr(NH 3 ) 5 X] 2+ (X = F, Cl, Br, I) series; r 0 and θ 0 are the equilibrium bond length and bond angle, respectively; k r and k θ are the force constants for the bonds and bond angles, respectively (1 kcal = J) Bond stretching k r / kcal mol -1 Å -2 r 0 /Å M F M Cl M Br M I Angle bending k ө / kcal mol -1 rad -2 θ 0 / rad cis trans cis trans N M N N M F N M Cl N M Br N M I van der Waals ε / kcal mol -1 r* / Å F H F N Cl H Cl N Br H Br N I H I N * Corresponding author. grubisic@chem.bg.ac.rs S67

2 S68 DJORDJEVIĆ et al. TABLE S-II. Comparison of the calculated partial atomic charges (esu); key: q = partial atomic charges, eq = equatorial or cis(x,nh 3 ), ax = axial or trans(x,nh 3 ), X=F, Cl, Br, I; Methods (as cited in the original publications): NPA = natural population analysis, MKS = Merz Kollman Singh scheme, NLDA = nonlocal density approximation, MEP = molecular electrostatic potential Complex q(m) q(n) q(h) q(f) q(cl) q(br) q(i) Meth. Ref. Published data [Co(NH 3 ) 6 ] NPA 1 [Co(NH 3 ) 6 ] MKS 1 [Co(NH 3 ) 6 ] [Co(NH 3 ) 6 ] [Co(NH 3 ) 5 F] [Co(NH 3 ) 5 F] [Cr(H 2 O) 6 ] NLDA 4 [Cr(H 2 O) 6 ] MEP 4 [Cr(H 2 O) 6 ] [Cr(H 2 O) 6 ] [CrF 6 ] NPA 6 [ZrF 6 ] MEP 7 [ZrCl 6 ] MEP 7 [ZrBr 6 ] MEP 7 [ZrI 6 ] MEP 7 This work [Cr(NH 3 ) 5 F] eq 0.41 eq 0.60 [Cr(NH 3 ) 5 Cl] eq 0.38 eq 0.44 [Cr(NH 3 ) 5 Br] eq 0.35 eq 0.34 [Cr(NH 3 ) 5 I] eq 0.30 eq 0.22 CSD REFCODES For structures with Cr F bonds ADOSOC, BAPPOX, BAVGOU, BAVGUA10, BIVVUX, BORWOU, BORWUA, BORWUA01, BUTDAV, DAFHOH, DEDCAQ, DIYFEW, DORZEP, DUCQIC, DULQAD, FEZXUD, FOJBAH, GAWBUC, IZOVEZ, KOMREJ, LEYDOJ, LEYDUP, LEYSEN, MPZFCR, OCOLIB, POFGEX, PUXPUT, QEXSES, SIXWOL, SUKHAH, TAZFCR, TETVUK, VAFDEN, VAFDIR, VIWMEU, VOLREU, YASHAB, YASHOP. For structures with Cr Cl bonds ABILUT, AMZCCR, BIJZOK, BIWPIH, CEDCRC, COKJAN, CUKPON, CUSBUN, DOHBEH, EGULOI, EKOCEM, EMIWIG, EMUNIJ, FAMVUK10, FUHCIU, GADTOU, JAQPEW, JATTED, JATVAB, JOFYIM, JOFYOS, JOMNAA, JOMNAA01, JOMNEE, KUGMAA, KUGMEE, LIJRAX, MATHIZ, MATHOF, MATHUL, MOLPUZ, PADSIW, PAZDUQ, PUWFAO, PYMECR, QISXIA, QOWZOS, QOWZUY, QOXBAH, RAKGIT, RUNRIB, RUNRIB01,

SUPPLEMENTARY MATERIAL S69 TEBDIO, TEZSIA, TEZSOG, TEZSUM, TEZTAT, TEZTEX, ULAYUC, UWEKEN, WATREO, WOGRUG, YISLIV, YISLOB, ZALZER, ULAYUC01, WEBCAJ, ACUCAE.

3 SUPPLEMENTARY MATERIAL S69 TEBDIO, TEZSIA, TEZSOG, TEZSUM, TEZTAT, TEZTEX, ULAYUC, UWEKEN, WATREO, WOGRUG, YISLIV, YISLOB, ZALZER, ULAYUC01, WEBCAJ, ACUCAE. For structures with Cr Br bonds BIWBEO, BOGDIL, CAGCIW, ESIMUO, IHEJOU, KUGMEE, MAMLER, PUDNUY, PUDPAG, PURCIO, UKEDEU, UKEDIY, VAGBIQ, VAQFAU, VAVNOV, VEFVEH, YIBWOV, TEDYIM. For structures with Cr I bonds BOGDOR, CPMINC, DAGNUW, JEKKEP, NATZIS, NMCPNC, ODAXIA, OFAKAI, PPNCCO, RAJXUV, SESYAQ, UGUBAZ, UKEDOE, UKEDUK, UKEFAS, UKEFOG, UKEFUM, VAZWAU, YEKLUW. Fig. S-1. Distribution of chromium(iii) halogen distances in the crystal structures retrieved from CSD (2013.): a) for Cr F bond lengths (Å); b) for Cr Cl bond lengths (Å); c) for Cr Br bond lengths (Å) and d) for Cr I bond length (Å). The data used in the derivation of the statistics are shown in black; data eliminated for any reason (see text) are shown in white. Note the difference in the scale for the x-axis between the upper and lower pair of charts.

4 S70 DJORDJEVIĆ et al. Fig. S-2. Symmetry coordinates for the normal vibrations of the C 4v -[CrN 5 X] skeleton. Definition of internal coordinates for skeletal vibrations: Metal ligand bonds: R i (i = 1,6). Octahedral angles: α ij (i, j = ligand atoms). a) S 1 (A 1 ) φ 1 (A 1 ) = (1/2)Δ(R 1 + R 2 + R 3 + R 4 ), b) S 2 (B 1 ) φ 2 (B 1 ) = (1/2)Δ(R 1 R 2 + R 3 R 4 ), c) S 3 (E) φ 3 (E a ) = (1/2) 1/2 Δ(R 2 R 4 ) φ 3 (E b ) = = (1/2) 1/2 Δ( R 1 R 3 ), d) S 4 (A 1 ) φ 4 (A 1 ) = ΔR 5, e) S 5 (A 1 ) φ 5 (A 1 ) = ΔR 6, f) S 6 (B 2 ) φ 6 (B 2 ) = = (1/2)Δ( α 12 α 23 + α 34 α 41 ), g) S 7 (E) φ 7 (E a ) = (1/2) 1/2 Δ(α 12 α 34 ) φ 7 (E b ) = (1/2) 1/2 Δ( α 23 α 41 ), h) S 8 (A 1 ) φ 8 (A 1 ) = (1/8) 1/2 Δ( α 15 α 16 + α 25 α 26 + α 35 α 36 + α 45 α 46 ), i) S 9 (B 1 ) φ 9 (B 1 ) = (1/8) 1/2 Δ( α 15 α 16 α 25 + α 26 + α 35 α 36 + α 45 + α 46 ), j) S 10 (E) φ 10 (E a ) = = (1/2)Δ(α 15 α 16 α 35 + α 36 ) φ 10 (E b ) = (1/2)Δ(α 25 α 26 α 45 + α 46 ), k) S 11 (E) φ 11 (E a ) = = (1/2)Δ(α 15 + α 16 α 35 + α 36 ) φ 11 (E b ) = (1/2)Δ(α 25 + α 26 α 45 + α 46 ); l) atom numbering.

5 SUPPLEMENTARY MATERIAL S71 TABLE S-III. Distribution of symmetry vibrations of [M(NH 3 ) 5 X] 2+ among the irreducible representations of the point group C 4v (Γ VIB = 12A 1 + 4A 2 + 7B 1 + 5B E); ν = stretching, δ = bending (deformation), ρ = rocking, s = symmetric, a = antisymmetric Motion A 1 A 2 B 1 B 2 E Skeletal a stretch S 1 : ν s (MN) eq S 2 : ν as (MN) eq S 3 : ν a (MN) eq S 4 : ν(mn) ax S 5 : ν(mx) Skeletal a bend S 8 : δ(mn 5 X) S 9 : δ(nmn) eq S 6 : δ(nmn) eq S 7 : δ(nmn) eq S 10 : δ(mn 5 X) S 11 : δ(mn 5 X) Sym. stretch ν s (NH) eq ν s (NH) eq ν s (NH) eq ν s (NH) ax As. stretch ν as (NH) eq ν as (NH) eq ν as (NH) eq ν as (NH) eq ν as (NH) eq ν as (NH) eq ν as (NH) ax Bend δ as (HNH) eq δ as (HNH) eq δ as (HNH) eq δ as (HNH) eq δ as (HNH) eq δ as (HNH) eq δ as (HNH) ax Rock ρ as (NH 3 ) eq ρ as (NH 3 ) eq ρ as (NH 3 ) eq ρ as (NH 3 ) eq ρ as (NH 3 ) eq ρ as (NH 3 ) eq ρ as (NH 3 ) ax δ s (NH 3 ) eq UMB b δ s (NH 3 ) eq δ s (NH 3 ) ax δ s (NH 3 ) eq Torsion τ as (NH 3 ) eq τ as (NH 3 ) ax τ as (NH 3 ) eq τ as (NH 3 ) eq a S i = Skeletal symmetry modes depicted in Fig. S-2; b UMB = Symmetrical NH 3 bending umbrella mode TABLE S-IV. Calculated a vibrational frequencies (cm -1 ) for [Cr(NH 3 ) 5 X] 2+ ; ν = stretching, δ = bending (deformation), ρ = rocking, s = symmetric, a = antisymmetric No. Principal assignment X = F X = Cl X = Br X = I Exp. CFF DFT Exp. CFF DFT Exp. CFF DFT Exp. CFF DFT 1 ν a (NH 3 ) ν a (NH 3 ) ν a (NH 3 ) ν a (NH 3 ) ν a (NH 3 ) ν a (NH 3 ) ν a (NH 3 ) ν a (NH 3 ) ν a (NH 3 ) ν a (NH 3 ) ν s (NH 3 ) ν s (NH 3 ) ν s (NH 3 ) ν s (NH 3 ) ν s (NH 3 ) δ a (H N H) δ a (H N H)

6 S72 DJORDJEVIĆ et al. TABLE S-IV. Continued No. Principal assignment X = F X = Cl X = Br X = I Exp. CFF DFT Exp. CFF DFT Exp. CFF DFT Exp. CFF DFT 18 δ a (H N H) δ a (H N H) δ a (H N H) δ a (H N H) δ a (H N H) δ a (H N H) δ a (H N H) δ a (H N H) δ s (H N H) δ s (H N H) δ s (H N H) δ s (H N H) δ s (H N H) ρ(nh 3 ) ρ(nh 3 ) ρ(nh 3 ) ρ(nh 3 ) ρ(nh 3 ) ρ(nh 3 ) ρ(nh 3 ) ρ(nh 3 ) ρ(nh 3 ) ρ(nh 3 ) ν a (Cr X) ν a (Cr N) ν a (Cr N) ν s (Cr N) ν s (Cr N) ν a (Cr N) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) δ(crn 5 X) a 8 Scaling factor for DFT (0.9833)

7 SUPPLEMENTARY MATERIAL S73 REFERENCES 1. W. R. Fawcett, M. Hromadova, G. A. Tsirlina, R. R. Nazmutdinov, J. Electroanal. Chem. 498 (2001) W. R. Fawcett, G. J. Chavis, M. Hromadová, Electrochim. Acta 53 (2008) R. R. Nazmutdinov, M.-Y. Rusanova, D. Van der Porten, G. A. Tsirlina, W. R. Fawcett, J. Phys. Chem. C 113 (2009) A. Bleuzen, F. Foglia, E. Furet, L. Helm, A. E. Merbach, J. Weber, J. Am. Chem. Soc. 118 (1996) M.-Y. Rusanova, G. A. Tsirlina, R. R. Nazmutdinov, W. R. Fawcett, J. Phys. Chem., A 109 (2005) C. Adamo, V. Barone, Theor. Chem. Acc. 105 (2000) J. Rak, M. Gutowski, P. Dokurno, H. V. Thanh, J. Blazejowski, J. Chem. Phys. 100 (1994) M. W. Wong, Chem. Phys. Lett. 256 (1996) 391.

Σχετικά έγγραφα

Electronic Supplementary Information:

Electronic Supplementary Information: 2 6 5 7 2 N S 3 9 6 7 5 2 S N 3 9 Scheme S. Atom numbering for thione and thiol tautomers of thioacetamide 3 0.6 0. absorbance 0.2 0.0 0.5 0.0 0.05 0.00 N 2 Ar km/mol