Pt(II) nitrile complexes: new insights on old complexes … · Web viewPt(II) nitrile complexes: new insights on old complexes from a combined experimental and theoretical study

Pt(II) nitrile complexes: new insights on old complexes from a combined

experimental and theoretical study.

R. Bertani, M. Mozzon, P.Sgarbossa, S.Tamburini, M. Casarin, G. Mangione, G. Casella,

A. Venzo, S. Rizzato, A.Albinati

S1

Supplementary Material

Table S1 Crystal data and structure refinement for trans-[PtCl2(NCPh)2]…………………………….… p. S3Table S2 Atomic coordinates (x104) and equivalent isotropic displacemen t parameters (Å2 x 103) for trans-[PtCl2(NCPh)2].……………………………………………………………….. p. S4Table S3 Hydrogen coordinates (x104) and isotropic displacement parameters (Å2 x103) for trans-[PtCl2(NCPh)2]. ………………………………………………………….…….. p. S4 Table S4 Anisotropic displacement parameters (Å2 x 103) for trans-[PtCl2(NCPh)2]………….………… p. S5Table S5 Bond lengths [Å] and angles [°] for trans-[PtCl2(NCPh)2]……………………………..……….. p. S6Table S6 Torsion angles [°] for trans-[PtCl2(NCPh)2]……………………………………………..……….. p. S7Table S7 LSQ planes for trans-[PtCl2(NCPh)2]…………………………………………………..………… p. S7Figure S1 ORTEP drawing of trans-[PtCl2(NCPh)2]……………………………………………...……….. p. S8Figure S2 Capped stick representation of the packing showing the phenyl rings stacking……………… p. S9Figure S3 A space filling representation of the molecular packing…………………………………………. p. S10Figure S4 Capped-stick diagram showing the shortest separation (Å) between phenyl rings and Cl….H contacts (Å)……………………………………………………………..……………….. p. S11Table S8 Crystal data and structure refinement for cis-[PtCl2(NCCH3)2]…………………..……………….. p. S12Table S9 Atomic coordinates (x104) and equivalent isotropic displacement parameters

(Å2 x103) for cis-[PtCl2(NCCH3)2]…………………………………………………………………….. p. S13Table S10 Hydrogen coordinates (x104) and isotropic displacement parameters (Å2 x 103) for cis-[PtCl2(NCCH3)2]……………………………………………………………………. p. S13Table S11 Anisotropic displacement parameters (Å2 x 103) for cis-[PtCl2(NCCH3)2]……………………….. p. S14Table S12 Bond lengths [Å] and angles [°] for cis-[PtCl2(NCCH3)2]………………………………………….. p. S14Table S13 Torsion angles [°] for cis-[PtCl2(NCCH3)2]…………………………………………………………… p. S15Table S14 LSQ planes for cis-[PtCl2(NCCH3)2]…………………………………………………………………. p. S15Figure S5 ORTEP drawing of cis-[PtCl2(NCCH3)2]…………………………………………………………….. p. S16 Figure S6 Capped stick representation of the packing viewed down the a axis……………………………. p. S17Figure S7 Space-filling representation of the molecular packing…………………………………………….. p. S18Figure S8 Capped-stick diagram showing short Cl….H contacts (Å)………………………………………… p. S19Table S15 Crystal data and structure refinement for cis-[PtCl2(NCPh)2]……………………………………. p. S20 Table S16 Atomic coordinates (x104) and equivalent isotropic displacement parameters (Å2 x103) for cis-[PtCl2(NCPh)2]………………………………………………………………………. p. S21Table S17 Hydrogen coordinates (x104) and isotropic displacement parameters (Å2 x 103) for cis-[PtCl2(NCPh)2]……………………………………………………………………….. p. S21Table S18 Anisotropic displacement parameters (Å2 x103) for cis-[PtCl2(NCPh)2]……………………………. p. S22Table S19 Bond lengths [Å] and angles [°] for cis-[PtCl2(NCPh)2]…………………………………… ……….. p. S23 Table S20 Torsion angles [°] for cis-[PtCl2(NCPh)2]………………………………………………………………. p. S24Table S21 LSQ planes for cis-[PtCl2(NCPh)2] ……………………………………………………………………. p. S25 Figure S9 ORTEP drawing of cis-[PtCl2(NCPh)2](Ellipsoids drawn at 50% probability)……………………... p. S27Figure S10 Capped stick representation of the packing…………………………………………………………… p. S28Figure S11 Space-filling model of the packing………………………………………………………………………. p. S29Figure S12a Capped-stick diagram showing short intermolecular Cl….H contacts (Å). ………………………. p. S30Figure S12b Capped-stick diagram showing short intermolecular contacts (Å) and the different interactions involving the Ph rings………………………………………………………………………………….. p. S31Tables S22-S24 Optimized coordinates ZSC BP86/TZ2P] and [ZSC COMSO (CH2Cl2; CH3CN) BP86/TZ2P] p. S32-34Tables S25-S26 Optimized coordinates [ZSC B3LYP/TZ2P] and [ZSC COSMO(CH3CN) B3LYP/TZ2P]…… p. S35-36Table S27 Summary of calculated maxs for the complexes with several protocols, on geometries ZSC BP86/TZ2P, ZSC COSMO BP86/TZ2P, ZSC B3LYP/TZ2P and ZSC COSMO B3LYP/TZ2P p. S37Tables S29-S40 Calculated (113C) …………………………………………………………………………………… p. S38-43Figure S13-S16 Orbitals involved in the electronic transitions and relevant % weights………………………… p. S44-46

S2

Table S1. Crystal data and structure refinement for trans-[PtCl2(NCPh)2].__________________________________________________________ Identification code transPh Empirical formula C14H10Cl2N2Pt Formula weight 472.23 Temperature 90(2) K Wavelength 0.71069 Å Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 5.7617(5) Å α = 115.960(1) °

b = 8.2347(7) Å β = 96.132(2) ° c = 8.4434(7) Å γ = 92.695(2) ° Volume 356.14(9) Å3 Z, Calculated density 1, 2.202 g/cm3 Absorption coefficient 10.210 mm-1 F(000) 220 Crystal size 0.06 x 0.05 x 0.04 mm θ range for data collection 2.71 ≤ θ ≤ 25.01°. Index ranges -6<=h<=6, -9<=k<=9, -10<=l<=10 Reflections collected / unique 2960 / 1243 [R(int) = 0.0185] Completeness to θ = 25.01 99.3% Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 1243 / 0 / 93 Goodness-of-fit on F2 1.062 Final R indices [I>2σ(I)] R1 = 0.0138, wR2 = 0.0342 R indices (all data) R1 = 0.0138, wR2 = 0.0342

S3

Largest diff. peak and hole 0.892 and -0.641 e/Å3

Table S2. Atomic coordinates (x104) and equivalent isotropic displacement parameters (Å2 x 103) for trans-[PtCl2(NCPh)2]. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________ x y z U(eq) ______________________________________________________________ Pt 0 0 0 17(1) Cl 1100(1) -2136(1) 909(1) 23(1) N(1) -1561(4) 1182(3) 2094(3) 20(1) C(1) -2504(5) 1865(4) 3305(4) 20(1) C(11) -3758(5) 2677(4) 4792(4) 18(1) C(12) -5896(5) 1767(4) 4751(4) 20(1) C(13) -7118(6) 2533(4) 6172(4) 24(1) C(14) -6267(6) 4181(4) 7610(4) 24(1) C(15) -4145(6) 5070(4) 7634(4) 23(1) C(16) -2869(5) 4330(4) 6243(4) 21(1)

Table S3. Hydrogen coordinates (x104) and isotropic displacement parameters

(Å2 x103) for trans-[PtCl2(NCPh)2]. _______________________________________________________________ x y z U(eq) ________________________________________________________________ H(12) -6480(30) 650(50) 3770(40) 24 H(13) -8430(60) 1980(30) 6169(4) 28 H(14) -7080(40) 4670(20) 8510(50) 29 H(15) -3590(20) 6160(50) 8590(40) 28 H(16) -1450(60) 4920(30) 6266(4) 25

Table S4. Anisotropic displacement parameters (Å2 x 103) for trans-[PtCl2(NCPh)2]. The anisotropic displacement factor exponent takes the form: -2 π2[ h2 a*2 U11 + ... + 2 h k a* b* U12 ] ___________________________________________________________________ U11 U22 U33 U23 U13 U12

___________________________________________________________________ Pt 21(1) 16(1) 14(1) 4(1) 7(1) 4(1) Cl 33(1) 19(1) 20(1) 8(1) 8(1) 8(1) N(1) 24(1) 20(1) 16(1) 7(1) 7(1) 5(1) C(1) 23(2) 19(1) 20(2) 10(1) 3(1) 4(1) C(11) 23(1) 20(1) 15(1) 9(1) 6(1) 8(1) C(12) 25(2) 17(2) 19(2) 8(1) 4(1) 5(1) C(13) 21(2) 29(2) 26(2) 16(1) 7(1) 6(1) C(14) 30(2) 30(2) 18(2) 12(1) 12(1) 15(1) C(15) 32(2) 20(2) 16(2) 6(1) 4(1) 9(1) C(16) 22(2) 20(1) 22(2) 10(1) 4(1) 4(1)

S4

S5

Table S5. Bond lengths [Å] and angles [°] for trans-[PtCl2(NCPh)2]. _____________________________________________________________ Pt-N(1)#1 1.949(3) Pt-N(1) 1.949(3) Pt-Cl 2.2953(7) Pt-Cl#1 2.2953(7) N(1)-C(1) 1.141(4) C(1)-C(11) 1.432(4) C(11)-C(16) 1.398(4) C(11)-C(12) 1.401(4) C(12)-C(13) 1.376(5) C(12)-H(12) 0.94 C(13)-C(14) 1.387(5) C(13)-H(13) 0.87 C(14)-C(15) 1.389(5) C(14)-H(14) 0.88 C(15)-C(16) 1.375(5) C(15)-H(15) 0.92 C(16)-H(16) 0.92 N(1)#1-Pt-Cl 89.48(8) N(1)-Pt-Cl 90.52(8) N(1)#1-Pt-Cl#1 90.52(8) N(1)-Pt-Cl#1 89.48(8) C(1)-N(1)-Pt 179.0(3) N(1)-C(1)-C(11) 178.0(3) C(16)-C(11)-C(12) 121.1(3) C(16)-C(11)-C(1) 120.9(3) C(12)-C(11)-C(1) 118.0(3) C(13)-C(12)-C(11) 118.6(3) C(13)-C(12)-H(12) 120.7 C(11)-C(12)-H(12) 120.7 C(12)-C(13)-C(14) 120.8(3) C(12)-C(13)-H(13) 119.6 C(14)-C(13)-H(13) 119.6 C(13)-C(14)-C(15) 120.0(3) C(13)-C(14)-H(14) 120.0 C(15)-C(14)-H(14) 120.0 C(16)-C(15)-C(14) 120.6(3) C(16)-C(15)-H(15) 119.7 C(14)-C(15)-H(15) 119.7 C(15)-C(16)-C(11) 118.9(3) C(15)-C(16)-H(16) 120.5 C(11)-C(16)-H(16) 120.5 _____________________________________________________________ Symmetry transformations used to generate equivalent atoms (#): 1 -x,-y,-z

S6

Table S6. Torsion angles [°] for trans-[PtCl2(NCPh)2]. ________________________________________________________________

Cl-Pt-N(1)-C(1) -106(15) N(1)-C(1)-C(11)-C(16) -170(9) N(1)-C(1)-C(11)-C(12) 10(10) C(16)-C(11)-C(12)-C(13) 0.0(4) C(1)-C(11)-C(12)-C(13) 180.0(3) C(11)-C(12)-C(13)-C(14) 0.7(4) C(12)-C(13)-C(14)-C(15) -0.6(5) C(13)-C(14)-C(15)-C(16) -0.1(5) C(14)-C(15)-C(16)-C(11) 0.8(4) C(12)-C(11)-C(16)-C(15) -0.7(4) ________________________________________________________________ Symmetry transformations used to generate equivalent atoms (#): 1 -x,-y,-z

Table S7. LSQ planes for trans-[PtCl2(NCPh)2]. _________________________________________________________________

Least-squares planes (x, y, z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 4.4175 (0.0043) x - 2.9644 (0.0028) y - 1.6192 (0.0082) z = 0.0000 (0.0000)

* 0.0000 (0.0000) Pt * 0.0000 (0.0000) Cl * 0.0000 (0.0000) N1 0.0182 (0.0049) C1 0.0903 (0.0063) C11

-1.0267 (0.0075) C16 Rms deviation of fitted atoms = 0.0000 2.6468 (0.0062) x - 6.4871 (0.0062) y + 5.8223 (0.0073) z = 0.0616 (0.0071) Angle to previous plane (with approximate esd) = 74.08 ( 0.07 ) * -0.0025 (0.0021) C11* -0.0023 (0.0020) C12* 0.0047 (0.0021) C13* -0.0022 (0.0022) C14* -0.0027 (0.0021) C15* 0.0050 (0.0021) C16

-0.0096 (0.0047) C1 Rms deviation of fitted atoms = 0.0034

S7

Fig. S1. ORTEP drawing of trans-[PtCl2(NCPh)2]. (Ellipsoids are drawn at 50% probability).

S8

Fig. S2. A capped stick representation of the packing showing the phenyl rings stacking.

S9

Fig. S3. A space filling representation of the molecular packing

S10

Fig. S4. Capped-stick diagram showing the shortest separation (Å) between phenyl rings and Cl….H contacts (Å).

S11

Table S8. Crystal data and structure refinement for cis-[PtCl2(NCCH3)2]._________________________________________________________

Identification code cisMe

Empirical formula C4H6Cl2N2Pt

Formula weight 348.10

Temperature 90(2) K

Wavelength 0.71073 Å

Crystal system, space group Monoclinic, P21/c

Unit cell dimensions a = 6.5318(4) Å α = 90°

b = 12.4056(7) Å β= 106.252(1)°

c = 10.2115(6) Å γ = 90°

Volume 794.38(8) Å3

Z, Calculated density 4, 2.911 g/cm3

Absorption coefficient 18.251 mm-1

F(000) 624

Crystal size 0.04 x 0.04 x 0.02 mm

θ range for data collection 3.25° ≤ θ ≤ 27.00°

Index ranges -8<=h<=8, -15<=k<=15, -12<=l<=13

Reflections collected / unique 7783 / 1722 [Rint = 0.0578]

Completeness to 2θ = 27.00 99.3%

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 1722 / 0 / 85

Goodness-of-fit on F2 1.113

Final R indices [I>2σ(I)] R1 = 0.0225, wR2 = 0.0598

R indices (all data) R1 = 0.0229, wR2 = 0.0602

Extinction coefficient 0.0024(3)

Largest diff. peak and hole 1.873 and -1.516 e/ Å3

S12

Table S9. Atomic coordinates (x104) and equivalent isotropic displacement parameters (Å2 x103) for cis-[PtCl2(NCCH3)2]. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________ x y z U(eq) ________________________________________________________________ Pt 7016(1) 2224(1) 7247(1) 10(1) Cl(1) 9450(2) 2918(1) 6269(1) 16(1) Cl(2) 6290(2) 3900(1) 7901(1) 14(1) N(1) 4972(6) 1607(3) 8149(4) 14(1) C(1) 3847(7) 1268(4) 8697(5) 14(1) C(11) 2386(8) 821(4) 9414(5) 17(1) N(2) 7551(6) 779(3) 6587(4) 12(1) C(2) 7765(7) -21(4) 6109(4) 12(1) C(21) 7961(8) -1031(4) 5452(5) 15(1)

Table S10. Hydrogen coordinates (x104) and isotropic displacement parameters (Å2 x 103) for cis-[PtCl2(NCCH3)2]. ________________________________________________________________ x y z U(eq) ________________________________________________________________ H(11A) 2128 58 9177 25 H(11B) 1033 1216 9144 25 H(11C) 3020 891 10400 25 H(21A) 6839 -1525 5544 23 H(21B) 9360 -1349 5884 23 H(21C) 7816 -904 4483 23

Table S11. Anisotropic displacement parameters (Å2 x 103) for cis-[PtCl2(NCCH3)2]. The anisotropic displacement factor exponent takes the form:-2π2[ h2 a*2 U11 + ... + 2hk a* b*U12]. _______________________________________________________________________ U11 U22 U33 U23 U13 U12

_______________________________________________________________________ Pt 12(1) 10(1) 11(1) -1(1) 8(1) 0(1) Cl(1) 21(1) 15(1) 20(1) -2(1) 17(1) -2(1) Cl(2) 19(1) 10(1) 16(1) -2(1) 11(1) 1(1) N(1) 19(2) 11(2) 15(2) -3(1) 10(2) 2(2) C(1) 16(2) 13(2) 16(2) 1(2) 9(2) 1(2) C(11) 17(2) 23(3) 16(2) 1(2) 14(2) 1(2) N(2) 15(2) 11(2) 13(2) 1(1) 10(1) -2(1) C(2) 10(2) 16(2) 14(2) -1(2) 8(2) 1(2) C(21) 19(2) 10(2) 18(2) -3(2) 9(2)

S13

Table S12. Bond lengths [Å] and angles [°] for cis-[PtCl2(NCCH3)2]. ________________________________________________________

Pt-N(1) 1.976(4) Pt-N(2) 1.980(4) Pt-Cl(1) 2.2701(12) Pt-Cl(2) 2.2734(10) N(1)-C(1) 1.123(6) C(1)-C(11) 1.464(6) N(2)-C(2) 1.132(6) C(2)-C(21) 1.443(6) N(1)-Pt-N(2) 90.84(15) N(1)-Pt-Cl(1) 178.17(12) N(2)-Pt-Cl(1) 88.95(11) N(1)-Pt-Cl(2) 89.63(11) N(2)-Pt-Cl(2) 177.18(11) Cl(1)-Pt-Cl(2) 90.67(4) C(1)-N(1)-Pt 178.0(4) N(1)-C(1)-C(11) 179.8(6) C(2)-N(2)-Pt 174.5(4) N(2)-C(2)-C(21) 177.6(5) Table S13. Torsion angles [°] for cis-[PtCl2(NCCH3)2].

______________________________________________

N(2)-Pt-N(1)-C(1) 119(11) Cl(1)-Pt-N(1)-C(1) 36(13) Cl(2)-Pt-N(1)-C(1) -63(11) N(1)-Pt-N(2)-C(2) 107(4) Cl(1)-Pt-N(2)-C(2) -75(4) Cl(2)-Pt-N(2)-C(2) 8(6) Pt-N(2)-C(2)-C(21) -22(15)

S14

Table S14. LSQ planes for cis-[PtCl2(NCCH3)2]. _____________________________________________________________

Least-squares planes (x, y, z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.3291 (0.0050) x - 1.5357 (0.0112) y + 6.8903 (0.0067) z = 6.9799 (0.0043)

* 0.0073 (0.0012) Pt * 0.0378 (0.0014) Cl1 * -0.0410 (0.0014) Cl2 * -0.0473 (0.0015) N2 * 0.0431 (0.0016) N1 -0.1828 (0.0056) C2 -0.4146 (0.0067) C21 0.0988 (0.0058) C1 0.1747 (0.0069) C11 Rms deviation of fitted atoms = 0.0381

S15

Fig. S5. ORTEP drawing of cis-[PtCl2(NCCH3)2]. (Ellipsoids are drawn at 50% probability).

S16

Fig. S6. A capped stick representation of the packing viewed down the a axis.

S17

Fig. S7. A space-filling representation of the molecular packing

S18

Fig. S8. Capped-stick diagram showing short Cl….H contacts (Å).

S19

Table S15. Crystal data and structure refinement for cis-[PtCl2(NCCH3)2].________________________________________________________________________ Identification code cisPh Empirical formula C14H10Cl2N2Pt Formula weight 472.23 Temperature 100(2) K Wavelength 0.71073 Å

Crystal system, space group Monoclinic, P21/c Unit cell dimensions a = 9.7912(11) Å α = 90° b = 11.7490(13) Å β = 103.9190(10)° c = 13.0098(14) Å γ = 90° Volume 1452.7(3) Å3

Z, Calculated density 4, 2.159 g/cm3

Absorption coefficient 10.013 mm-1

F(000) 880 Crystal size 0.20 x 0.10 x 0.06 mm θ range for data collection 2.14° ≤ θ ≤ 29.37° Limiting indices -13<=h<=13, -15<=k<=16, -17<=l<=17 Reflections collected / unique 17235 / 3758 [R(int) = 0.0251] Completeness to θ = 29.37 94.0 % Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 3758 / 0 / 202 Goodness-of-fit on F2 1.184 Final R indices [I>2σ(I)] R1 = 0.0230, wR2 = 0.0510 R indices (all data) R1 = 0.0252, wR2 = 0.0515

S20

Largest diff. peak and hole 2.339 and -1.422 e/ Å3

Table S16. Atomic coordinates (x104) and equivalent isotropic displacement parameters (Å2 x103) for cis-[PtCl2(NCPh)2]. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ________________________________________________________________ x y z U(eq) ________________________________________________________________ Pt -5530(1) 189(1) 6179(1) 13(1) Cl(1) -7814(1) -271(1) 5458(1) 20(1) Cl(2) -5069(1) -1611(1) 6825(1) 19(1) N(1) -3576(3) 667(3) 6789(2) 18(1) C(1) -2493(4) 1082(3) 7054(3) 19(1) C(11) -1174(4) 1663(3) 7396(3) 17(1) C(12) -41(4) 1387(3) 6969(3) 20(1) C(13) 1201(4) 1993(4) 7290(3) 22(1) C(14) 1308(4) 2863(4) 8033(3) 22(1) C(15) 180(4) 3126(3) 8458(3) 22(1) C(16) -1080(4) 2537(3) 8144(3) 20(1) N(2) -5959(3) 1757(3) 5660(3) 18(1) C(2) -6264(4) 2657(3) 5368(3) 21(1) C(21) -6731(5) 3773(3) 5019(3) 23(1) C(22) -6306(5) 4288(4) 4180(3) 25(1) C(23) -6839(6) 5362(4) 3850(4) 32(1) C(24) -7759(7) 5895(4) 4331(4) 42(1) C(25) -8173(8) 5380(5) 5160(5) 55(2) C(26) -7673(7) 4310(4) 5503(4) 44(1)

Table S17. Hydrogen coordinates (x104) and isotropic displacement parameters (Å2 x 103) for cis-[PtCl2(NCPh)2]. ________________________________________________________________ x y z U(eq) ________________________________________________________________ H(12) -120(70) 820(60) 6510(50) 53 H(13) 2000(70) 1790(50) 7020(50) 53 H(14) 2150(70) 3280(50) 8280(50) 53 H(15) 210(60) 3660(60) 8940(50) 53 H(16) -1870(60) 2700(50) 8410(50) 53 H(22) -5660(70) 3910(50) 3870(50) 53 H(23) -6500(60) 5760(50) 3230(50) 53 H(24) -8110(60) 6590(60) 4090(50) 53 H(25) -8850(70) 5760(60) 5510(50) 53 H(26) -8000(60) 3950(50) 6060(50) 53

S21

Table S18. Anisotropic displacement parameters (Å2 x103) for cis-[PtCl2(NCPh)2]. The anisotropic displacement factor exponent takes the form: -2π2[ h2a*2U11 + ...+ 2hka*b*U12].

______________________________________________________________________ U11 U22 U33 U23 U13 U12

______________________________________________________________________ Pt 13(1) 12(1) 13(1) -1(1) 4(1) -1(1) Cl(1) 15(1) 21(1) 22(1) 2(1) 2(1) -2(1) Cl(2) 18(1) 14(1) 24(1) 3(1) 6(1) 2(1) N(1) 18(2) 17(2) 18(2) -2(1) 5(1) -1(1) C(1) 20(2) 17(2) 20(2) -1(1) 5(1) 2(1) C(11) 15(2) 16(2) 19(2) 2(1) 2(1) 0(1) C(12) 20(2) 18(2) 22(2) 1(2) 5(2) 3(1) C(13) 17(2) 27(2) 22(2) 2(2) 7(2) 2(2) C(14) 15(2) 23(2) 27(2) 2(2) 1(2) -3(2) C(15) 22(2) 17(2) 24(2) -4(2) 3(2) -2(2) C(16) 16(2) 19(2) 26(2) -4(2) 6(2) 0(1) N(2) 21(2) 16(2) 18(2) -1(1) 7(1) -2(1) C(2) 26(2) 20(2) 19(2) -3(2) 7(2) -5(2) C(21) 33(2) 14(2) 20(2) 0(1) 5(2) -1(2) C(22) 31(2) 22(2) 24(2) 1(2) 9(2) -4(2) C(23) 53(3) 24(2) 20(2) 4(2) 12(2) 2(2) C(24) 76(4) 22(2) 30(3) 9(2) 16(3) 14(2) C(25) 103(5) 33(3) 42(3) 11(2) 40(3) 34(3) C(26) 81(4) 29(3) 31(3) 12(2) 31(3) 19(3)

S22

Table S19. Bond lengths [Å] and angles [°] for cis-[PtCl2(NCPh)2]. _____________________________________________________________ Pt-N(1) 1.968(3)

Pt-N(2) 1.972(3)

Pt-Cl(1) 2.2727(9)

Pt-Cl(2) 2.2806(9)

N(1)-C(1) 1.142(5)

C(1)-C(11) 1.434(5)

C(11)-C(12) 1.394(5)

C(11)-C(16) 1.403(5)

C(12)-C(13) 1.384(6)

C(12)-H(12) 0.88(7)

C(13)-C(14) 1.393(6)

C(13)-H(13) 0.97(6)

C(14)-C(15) 1.384(6)

C(14)-H(14) 0.94(6)

C(15)-C(16) 1.388(6)

C(15)-H(15) 0.88(6)

C(16)-H(16) 0.94(6)

N(2)-C(2) 1.138(5)

C(2)-C(21) 1.427(6)

C(21)-C(26) 1.387(7)

C(21)-C(22) 1.396(6)

C(22)-C(23) 1.394(6)

C(22)-H(22) 0.93(6)

C(23)-C(24) 1.365(7)

C(23)-H(23) 1.05(6)

C(24)-C(25) 1.381(8)

C(24)-H(24) 0.91(7)

C(25)-C(26) 1.384(7)

C(25)-H(25) 1.00(6)

C(26)-H(26) 0.95(6)

N(1)-Pt-N(2) 88.75(14)N(1)-Pt-Cl(1) 177.17(10)N(2)-Pt-Cl(1) 88.46(10)N(1)-Pt-Cl(2) 91.67(10)N(2)-Pt-Cl(2) 178.06(9)Cl(1)-Pt-Cl(2) 91.10(3)C(1)-N(1)-Pt 170.1(3)N(1)-C(1)-C(11) 176.7(4)C(12)-C(11)-C(16) 121.5(4)C(12)-C(11)-C(1) 120.7(4)C(16)-C(11)-C(1) 117.8(3)C(13)-C(12)-C(11) 119.0(4)C(13)-C(12)-H(12) 121(4)C(11)-C(12)-H(12) 120(4)C(12)-C(13)-C(14) 120.1(4)C(12)-C(13)-H(13) 119(4)C(14)-C(13)-H(13) 121(4)C(15)-C(14)-C(13) 120.5(4)C(15)-C(14)-H(14) 118(4)C(13)-C(14)-H(14) 122(4)C(14)-C(15)-C(16) 120.6(4)C(14)-C(15)-H(15) 123(4)C(16)-C(15)-H(15) 116(4)C(15)-C(16)-C(11) 118.3(4)C(15)-C(16)-H(16) 123(4)C(11)-C(16)-H(16) 119(4)C(2)-N(2)-Pt 177.0(3)N(2)-C(2)-C(21) 176.3(4)C(26)-C(21)-C(22) 120.9(4)C(26)-C(21)-C(2) 118.0(4)C(22)-C(21)-C(2) 121.0(4)C(23)-C(22)-C(21) 118.2(4)C(23)-C(22)-H(22) 123(4)C(21)-C(22)-H(22) 119(4)C(24)-C(23)-C(22) 120.9(4)C(24)-C(23)-H(23) 121(3)C(22)-C(23)-H(23) 118(3)C(23)-C(24)-C(25) 120.5(5)C(23)-C(24)-H(24) 120(4)C(25)-C(24)-H(24) 120(4)C(24)-C(25)-C(26) 120.1(5)C(24)-C(25)-H(25) 121(4)C(26)-C(25)-H(25) 119(4)C(25)-C(26)-C(21) 119.3(5)C(25)-C(26)-H(26) 119(4)C(21)-C(26)-H(26) 121(4)

S23

Table S20. Torsion angles [°] for cis-[PtCl2(NCPh)2]. ________________________________________________________________ N(2)-Pt-N(1)-C(1) -13.5(18) Cl(1)-Pt-N(1)-C(1) -23(3) Cl(2)-Pt-N(1)-C(1) 168.4(18) Pt-N(1)-C(1)-C(11) 46(9) N(1)-C(1)-C(11)-C(12) -146(7) N(1)-C(1)-C(11)-C(16) 33(7) C(16)-C(11)-C(12)-C(13) -0.2(6) C(1)-C(11)-C(12)-C(13) 177.8(4) C(11)-C(12)-C(13)-C(14) 0.2(6) C(12)-C(13)-C(14)-C(15) 0.2(6) C(13)-C(14)-C(15)-C(16) -0.6(6) C(14)-C(15)-C(16)-C(11) 0.6(6) C(12)-C(11)-C(16)-C(15) -0.2(6) C(1)-C(11)-C(16)-C(15) -178.2(4) N(1)-Pt-N(2)-C(2) -145(6) Cl(1)-Pt-N(2)-C(2) 35(6) Cl(2)-Pt-N(2)-C(2) -42(8) Pt-N(2)-C(2)-C(21) 1(12) N(2)-C(2)-C(21)-C(26) 31(7) N(2)-C(2)-C(21)-C(22) -146(7) C(26)-C(21)-C(22)-C(23) 0.8(7) C(2)-C(21)-C(22)-C(23) 177.7(4) C(21)-C(22)-C(23)-C(24) -0.4(7) C(22)-C(23)-C(24)-C(25) 0.4(9) C(23)-C(24)-C(25)-C(26) -0.9(11) C(24)-C(25)-C(26)-C(21) 1.3(11) C(22)-C(21)-C(26)-C(25) -1.2(9) C(2)-C(21)-C(26)-C(25) -178.2(6)

S24

Table S21. LSQ planes for cis-[PtCl2(NCPh)2]. _____________________________________________________________ Least-squares planes (x, y, z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 4.4936 (0.0065) x + 3.0310 (0.0087) y + 12.1723 (0.0036) z = 10.0810 (0.0038) * -0.0178 (0.0010) Pt * -0.0077 (0.0012) Cl1 * 0.0157 (0.0011) Cl2 * -0.0087 (0.0013) N1 * 0.0185 (0.0014) N2 -0.0461 (0.0049) C1 -0.0474 (0.0056) C11 0.0735 (0.0050) C2 0.1962 (0.0057) C21 Rms deviation of fitted atoms = 0.0144 1.4674 (0.0162) x - 7.7450 (0.0148) y + 8.8361 (0.0162) z = 5.0753 (0.0153) Angle to previous plane (with approximate esd) = 67.19 ( 0.09 )

* -0.0008 (0.0027) C11 * 0.0023 (0.0028) C12

* -0.0009 (0.0029) C13 * -0.0021 (0.0029) C14 * 0.0037 (0.0030) C15 * -0.0022 (0.0029) C16 -0.0459 (0.0062) C1 Rms deviation of fitted atoms = 0.0022

- 4.4936 (0.0065) x + 3.0310 (0.0087) y + 12.1723 (0.0036) z = 10.0810 (0.0038) Angle to previous plane (with approximate esd) = 67.19 ( 0.09 ) * -0.0178 (0.0010) Pt * -0.0077 (0.0012) Cl1 * 0.0157 (0.0011) Cl2 * -0.0087 (0.0013) N1 * 0.0185 (0.0014) N2 0.0735 (0.0050) C2 0.1962 (0.0057) C21 Rms deviation of fitted atoms = 0.0144

S25

6.1644 (0.0197) x + 4.9847 (0.0252) y + 6.2486 (0.0290) z = 0.8632 (0.0296) Angle to previous plane (with approximate esd) = 68.05 ( 0.14 ) * 0.0042 (0.0035) C21 * -0.0011 (0.0034) C22 * -0.0001 (0.0038) C23 * -0.0016 (0.0046) C24 * 0.0047 (0.0052) C25 * -0.0059 (0.0046) C26 -0.0457 (0.0076) C2 Rms deviation of fitted atoms = 0.0036

S26

Fig. S9. ORTEP drawing of cis-[PtCl2(NCPh)2]. (Ellipsoids drawn at 50% probability).

S27

Fig. S10. A capped stick representation of the packing.

S28

Fig. S11. A space-filling model of the packing.

S29

Fig. S12a. Capped-stick diagram showing short intermolecular Cl….H contacts (Å).

S30

Fig. S12b. Capped-stick diagram showing short intermolecular contacts (Å) and the different interactions involving the Ph rings.

S31

Table S22. Optimized coordinates [ZSC BP86/TZ2P]

cis-[PtCl2(NCCH3)2]

15

Pt 0.00000 0.00000 0.00000Cl -0.02332 2.28547 0.00000Cl 2.28545 0.00000 0.00000N -1.95926 0.07745 -0.00056N 0.09644 -1.95849 0.02382C -3.10281 0.26712 -0.00822C 0.29626 -3.09956 0.05788C -4.52627 0.54556 -0.02373C 0.58830 -4.51958 0.10580H -5.10039 -0.38767 -0.08928H -4.77306 1.17555 -0.88892H -4.81525 1.07708 0.89282H -0.30955 -5.10582 -0.12872H 0.94334 -4.79762 1.10728H 1.37114 -4.76204 -0.62529

trans-[PtCl2(NCCH3)2]

15

Pt 0.00000 0.00000 0.00000Cl -2.33182 0.00000 -0.07963Cl 2.33353 0.00000 0.00000N 0.00223 1.92422 0.10956N 0.00079 -1.92330 0.12071C 0.01216 3.05684 0.34124C 0.00708 -3.05534 0.35532C 0.02940 4.46114 0.70013C 0.01807 -4.45897 0.71704H -0.97595 4.77908 1.00610H 0.35753 5.07456 -0.14832H 0.72223 4.61370 1.53894H -1.01067 -4.82082 0.84280H 0.51701 -5.05411 -0.05804H 0.55850 -4.58531 1.66525

cis-[PtCl2(NCPh)2]

29

Pt 0.00000 0.00000 0.00000Cl 0.00000 2.28500 0.00000Cl 2.28401 -0.00881 0.00000N -1.95460 0.10064 0.02961N 0.08521 -1.95280 -0.09983C -3.09118 0.34577 0.06449C 0.30804 -3.08268 -0.26269C -4.46667 0.69805 0.06599C 0.60669 -4.44609 -0.52542C -4.96039 1.5324 -0.95714C -6.30124 1.90318 -0.95240C -7.15329 1.45222 0.06009C -6.66357 0.62529 1.07559C -5.32501 0.24425 1.08608C 0.33712 -4.97797 -1.80229C 0.66513 -6.30137 -2.07839C 1.25810 -7.09892 -1.09513C 1.52357 -6.57249 0.17250C 1.20187 -5.25043 0.46548H -4.28415 1.88424 -1.73336H -6.68170 2.55031 -1.74100H -8.20128 1.74892 0.05951H -7.32710 0.28018 1.86681H -4.93242 -0.39129 1.87713H -0.11386 -4.34364 -2.56264H 0.46368 -6.70956 -3.06742H 1.51821 -8.13253 -1.31930H 1.98926 -7.19393 0.93559H 1.41404 -4.82771 1.44515

trans-[PtCl2(NCPh)2]

29

Pt 0.00000 0.00000 0.00000Cl -2.33486 0.00000 -0.00515Cl 2.33551 0.00000 0.00000N 0.00075 1.56037 1.12392N 0.00339 -1.57543 -1.10224C 0.00485 2.48886 1.81927C 0.00895 -2.53823 -1.74929C 0.01593 3.61631 2.68146C 0.02061 -3.72364 -2.52955C -1.07943 4.50181 2.69495C -1.05832 5.60079 3.54814C 0.03896 5.82191 4.38579C 1.12528 4.94195 4.37165C 1.12351 3.83932 3.52311C 1.17792 -4.52641 -2.56126C 1.17991 -5.69153 -3.32174C 0.04448 -6.05982 -4.04963C -1.10243 -5.26088 -4.01906C -1.12419 -4.09345 -3.26228H -1.92836 4.31659 2.04018H -1.90283 6.28774 3.55994H 0.04746 6.68330 5.05243H 1.97860 5.11507 5.02522H 1.96284 3.14738 3.50062H 2.05472 -4.22703 -1.99082H 2.07190 -6.31526 -3.34605H 0.05338 -6.97330 -4.64287H -1.98527 -5.54903 -4.58722H -2.01094 -3.46402 -3.22744

S32

Table S23. Optimized coordinates [ZSC COMSO (CH2Cl2) BP86/TZ2P]

cis-[PtCl2(NCCH3)2]

15

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.304794Cl 2.304931 0.000000 -0.013557N -1.962000 0.033106 0.038745N 0.027415 -0.113055 -1.959711C -3.117651 0.058080 0.103503C 0.083075 -0.294926 -3.101796C -4.560008 0.078652 0.195176C 0.158846 -0.553865 -4.521491H -4.996002 0.059705 -0.810909H -4.902790 -0.800732 0.754332H -4.885724 0.988409 0.714269H -0.817745 -0.371862 -4.985929H 0.446739 -1.600307 -4.682286H 0.907233 0.102682 -4.981446


15

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.337029Cl 0.108136 0.000000 -2.334586N -0.138758 -1.936137 -0.009649N -0.145584 1.935467 -0.008009C -0.460153 -3.047436 -0.041618C -0.469925 3.045933 -0.030410C -0.929178 -4.412545 -0.088572C -0.945503 4.409260 -0.062169H -1.284599 -4.711031 0.905418H -0.123890 -5.083685 -0.407672H -1.761566 -4.475442 -0.801837H -1.125662 4.760196 0.961206H -0.210516 5.059505 -0.550091H -1.888322 4.439158 -0.624445

cis-[PtCl2(NCPh)2]

29

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.301512Cl 2.302058 0.000000 -0.000362N -1.955586 -0.109378 0.059076N 0.064046 0.030864 -1.957165C -3.088390 -0.304259 0.226713C 0.234808 0.064388 -3.105619C -4.453121 -0.617960 0.453443C 0.488641 0.077929 -4.501135C -5.320335 0.332226 1.027240C -6.640741 -0.024991 1.286213C -7.097934 -1.310359 0.974715C -6.235706 -2.248977 0.397151C -4.911819 -1.912411 0.133480C -0.057561 1.088783 -5.316465C 0.229755 1.089973 -6.678653C 1.052085 0.099259 -7.227125C 1.592427 -0.903257 -6.414361C 1.315787 -0.922866 -5.050864H -4.952878 1.326754 1.268041H -7.315398 0.701247 1.735006H -8.130769 -1.582985 1.184812H -6.593019 -3.248244 0.156556H -4.227973 -2.634385 -0.306840H -0.690697 1.856646 -4.878358H -0.186976 1.868297 -7.314803H 1.273410 0.108548 -8.293046H 2.232205 -1.672074 -6.842940H 1.731668 -1.694069 -4.406799


29

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.336686Cl 0.016518 0.000000 -2.336769 N -0.191935 -1.925764 -0.002134 N 0.142098 1.929855 -0.000108 C -0.347311 -3.075936 -0.004031 C 0.184326 3.089613 -0.000566 C -0.554188 -4.478759 -0.010111 C 0.216182 4.507100 -0.003369 C -0.141376 -5.252224 1.093522 C -0.361486 -6.626498 1.078797 C -0.986329 -7.228500 -0.019059 C -1.393791 -6.457493 -1.113421 C -1.181770 -5.082023 -1.119088 C -0.180626 5.207979 -1.160464 C -0.160808 6.599535 -1.150949 C 0.249726 7.290359 -0.005377 C 0.645451 6.591175 1.140371 C 0.631880 5.199466 1.151893 H 0.342279 -4.772691 1.941191 H -0.045378 -7.229742 1.927496 H -1.156992 -8.303958 -0.021723 H -1.879550 -6.929030 -1.965414 H -1.494681 -4.471743 -1.962966 H -0.498908 4.659560 -2.043878 H -0.468174 7.146596 -2.040022 H 0.260886 8.379187 -0.005329 H 0.964948 7.132115 2.028890 H 0.935800 4.644911 2.036517

S33

Table S24. Optimized coordinates [ZSC COSMO(CH3CN) BP86/TZ2P]

cis-[PtCl2(NCCH3)2]

15

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.306787Cl 2.307173 0.000000 -0.012886 N -1.961734 0.038147 0.013596 N 0.012264 -0.141629 -1.958857 C -3.118636 0.072623 0.007011 C 0.017342 -0.383612 -3.091098 C -4.562397 0.103454 -0.008225 C 0.023154 -0.725744 -4.494292 H -4.924702 -0.282508 -0.969264 H -4.951186 -0.524884 0.802328 H -4.913943 1.133710 0.125696 H -1.007151 -0.881879 -4.837030 H 0.592688 -1.653519 -4.633406 H 0.485336 0.077974 -5.079171


15

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.336458Cl 0.096398 0.000000 -2.334069 N -0.107661 -1.940669 -0.007740 N -0.151834 1.937365 -0.001188 C -0.400700 -3.060196 -0.028525 C -0.465204 3.051727 -0.007756 C -0.836270 -4.436433 -0.057485 C -0.922520 4.421179 -0.018779 H -1.194958 -4.725261 0.938337 H -0.012353 -5.093741 -0.356456 H -1.659699 -4.531138 -0.777474 H -1.109203 4.754437 1.009260 H -0.173490 5.070088 -0.486752 H -1.859115 4.474066 -0.589585

cis-[PtCl2(NCPh)2] 29

Pt 0.000000 0.000000 0.000000 Cl 0.000000 0.000000 2.304541 Cl 2.304142 0.000000 0.007480 N -1.958448 -0.010904 0.058064 N 0.064116 0.016952 -1.958320 C -3.108337 -0.042634 0.220968 C 0.232549 0.049159 -3.107321 C -4.508358 -0.081259 0.444907 C 0.463626 0.087384 -4.506318 C -5.139753 1.013056 1.070931 C -6.511137 0.963937 1.301836 C -7.250531 -0.159426 0.915662 C -6.620332 -1.244415 0.295585 C -5.249571 -1.215473 0.056254 C 0.118826 1.239839 -5.241169 C 0.371458 1.272428 -6.609536 C 0.959585 0.171886 -7.243863 C 1.300149 -0.970460 -6.511103 C 1.056620 -1.022749 -5.141991 H -4.553888 1.879095 1.368770 H -7.004308 1.804630 1.785796 H -8.323114 -0.190243 1.100262 H -7.198753 -2.116945 -0.001163 H -4.747575 -2.053474 -0.421127 H -0.334958 2.088723 -4.735823 H 0.109441 2.158988 -7.183313 H 1.155235 0.205741 -8.314321 H 1.758668 -1.823334 -7.007686 H 1.320283 -1.903533 -4.560966


29

Pt -0.071751 0.001800 -0.055713Cl 0.453572 2.271010 0.128250Cl -0.597438 -2.267006 -0.240275 N -1.226915 0.148787 1.490909 N 1.118854 -0.147127 -1.574883 C -1.887059 0.240842 2.440998 C 1.869230 -0.244523 -2.455076 C -2.682421 0.363798 3.607527 C 2.799378 -0.366797 -3.517239 C -2.392669 1.383166 4.537629 C -3.173590 1.496675 5.683701 C -4.232191 0.608809 5.905159 C -4.517866 -0.400143 4.978622 C -3.748761 -0.531725 3.826279 C 3.803698 0.609941 -3.675745 C 4.724001 0.473720 -4.710784 C 4.648289 -0.619468 -5.581018 C 3.648155 -1.585217 -5.421999 C 2.718554 -1.468452 -4.393033 H -1.567568 2.067193 4.353568 H -2.955077 2.280016 6.406418 H -4.837789 0.703704 6.804637 H -5.342208 -1.087822 5.155061 H -3.959447 -1.312467 3.099377 H 3.852820 1.453352 -2.991250 H 5.503629 1.221876 -4.837728 H 5.373207 -0.719891 -6.386771 H 3.593479 -2.433665 -6.100719 H 1.938400 -2.213642 -4.257234

S34

Table S25. Optimized coordinates [ZSC B3LYP/TZ2P]

cis-[PtCl2(NCCH3)2]

15

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.293712Cl 2.290938 0.000000 -0.087448N -1.993648 0.033325 0.027060N -0.047426 -0.119899 -1.989823C -3.138329 0.055133 0.013625C -0.107222 -0.307641 -3.117757C -4.589857 0.060869 -0.020958C -0.201792 -0.597128 -4.537321H -4.936121 0.026693 -1.054271H -4.975439 0.964629 0.450166H -4.977313 -0.808563 0.509736H -1.215100 -0.405129 -4.890708H 0.039928 -1.645739 -4.712989H 0.492959 0.025336 -5.099802

trans-[PtCl2(NCCH3)2]15

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 -2.345533Cl -0.084886 0.000000 2.345159N -0.068615 1.945771 0.000461N -0.074484 -1.942668 -0.002177C -0.122272 3.085948 -0.000481C -0.130766 -3.082691 -0.005082C -0.205216 4.531756 -0.002468C -0.216707 -4.528317 -0.010161H -0.437035 4.884750 -1.006788H 0.744341 4.959375 0.317465H -0.989643 4.854499 0.681572H -0.264040 -4.890011 -1.036745H 0.657428 -4.954444 0.480896H -1.113347 -4.843666 0.522799


Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.291809Cl 2.290423 0.000000 -0.081784 N -1.994837 -0.011837 -0.025672 N -0.095655 0.017075 -1.991588 C -3.125894 -0.015127 -0.227119 C -0.333297 0.028510 -3.115697 C -4.511821 -0.024497 -0.556370 C -0.708357 0.044569 -4.489967 C -5.319327 1.076223 -0.249088 C -6.653169 1.072088 -0.622694 C -7.188215 -0.018536 -1.297832 C -6.388800 -1.114868 -1.598732 C -5.053752 -1.125126 -1.231736 C -1.379133 1.158443 -5.010182 C -1.790638 1.155177 -6.332334 C -1.539331 0.052519 -7.140074 C -0.869456 -1.051696 -6.626671 C -0.451350 -1.062866 -5.306080 H -4.896809 1.921353 0.271951 H -7.276181 1.922182 -0.389157 H -8.228353 -0.014493 -1.589390 H -6.806035 -1.962145 -2.121920 H -4.427064 -1.971929 -1.465546 H -1.573864 2.010274 -4.376872 H -2.309719 2.012937 -6.732973 H -1.865985 0.053853 -8.169752 H -0.674612 -1.906762 -7.256220 H 0.066205 -1.918309 -4.900389


29

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.345998Cl 0.136292 0.000000 -2.340975 N -0.033749 -1.940710 0.003261 N -0.031837 1.940716 0.004221 C -0.060365 -3.085224 0.013987 C -0.056028 3.085194 0.021728 C -0.060980 -4.504991 0.040255 C -0.055895 4.504854 0.052163 C 1.102736 -5.175505 0.430804 C 1.117138 -6.558912 0.454023 C -0.018309 -7.274412 0.093241 C -1.175543 -6.607244 -0.291464 C -1.205402 -5.223161 -0.321121 C -1.200212 5.224378 -0.306942 C -1.170055 6.608296 -0.272856 C -0.012702 7.274034 0.114069 C 1.122746 6.557181 0.472182 C 1.108094 5.173890 0.444261 H 1.976374 -4.606987 0.709635 H 2.014930 -7.078037 0.753059 H -0.000884 -8.354015 0.111658 H -2.055610 -7.167004 -0.569992 H -2.098356 -4.696268 -0.620421 H -2.093445 4.698621 -0.607368 H -2.050261 7.169038 -0.548916 H 0.004713 8.353562 0.136512 H 2.020665 7.075061 0.773079 H 1.981643 4.604298 0.721248

S35

Table S26.Optimized coordinates [ZSC COSMO(CH3CN) B3LYP/TZ2P]

cis-[PtCl2(NCCH3)2]

15

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.293712Cl 2.290938 0.000000 -0.087448 N -1.993648 0.033325 0.027060 N -0.047426 -0.119899 -1.989823 C -3.138329 0.055133 0.013625 C -0.107222 -0.307641 -3.117757 C -4.589857 0.060869 -0.020958 C -0.201792 -0.597128 -4.537321 H -4.936121 0.026693 -1.054271 H -4.975439 0.964629 0.450166 H -4.977313 -0.808563 0.509736 H -1.215100 -0.405129 -4.890708 H 0.039928 -1.645739 -4.712989 H 0.492959 0.025336 -5.099802


15

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.350977Cl 0.017149 0.000000 -2.350606 N -0.034833 -1.958660 0.003883 N -0.023875 1.958809 0.004105 C -0.100773 -3.099516 0.016399 C -0.081475 3.100337 0.016865 C -0.194898 -4.538980 0.041796 C -0.161844 4.540705 0.042499 H -1.086203 -4.829673 0.595330 H 0.687567 -4.950556 0.528025 H -0.260803 -4.915998 -0.977012 H -0.936046 4.844155 0.745121 H 0.796451 4.950720 0.355762 H -0.409489 4.907574 -0.951845


Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.319270Cl 2.318758 0.000000 -0.048773 N -1.990550 0.022305 -0.062281 N -0.104216 -0.006211 -1.989077 C -3.096192 0.076448 -0.368729 C -0.435316 -0.019563 -3.088783 C -4.441828 0.155496 -0.817947 C -0.917667 -0.025660 -4.425298 C -5.174570 1.333033 -0.620463 C -6.462453 1.421741 -1.122346 C -7.019309 0.351110 -1.814756 C -6.291576 -0.819293 -2.005889 C -5.002598 -0.926412 -1.510590 C -1.596957 1.101002 -4.909357 C -2.121670 1.078301 -6.190666 C -1.974058 -0.053471 -6.986392 C -1.297305 -1.169725 -6.504847 C -0.765786 -1.165271 -5.225457 H -4.732604 2.160520 -0.088809 H -7.030593 2.327748 -0.978383 H -8.022046 0.429501 -2.207856 H -6.727667 -1.646634 -2.544317 H -4.430009 -1.828296 -1.659220 H -1.710658 1.972367 -4.283933 H -2.648256 1.941506 -6.567764 H -2.389640 -0.066120 -7.983030 H -1.187984 -2.045387 -7.125826 H -0.246227 -2.028927 -4.842312


29

Pt 0.000000 0.000000 0.000000Cl 0.000000 0.000000 2.348768Cl 0.113010 0.000000 -2.346755 N -0.258246 1.943046 -0.030111 N -0.249459 -1.946116 -0.027888 C -0.827364 2.933643 -0.138873 C -0.830802 -2.930214 -0.131608 C -1.701157 4.036824 -0.307890 C -1.733331 -4.012746 -0.282199 C -3.074310 3.749363 -0.328375 C -3.978648 4.775461 -0.533535 C -3.522412 6.077332 -0.713706 C -2.159834 6.358805 -0.686029 C -1.238951 5.343180 -0.484193 C -1.312681 -5.337004 -0.423294 C -2.265658 -6.328145 -0.596324 C -3.618792 -6.004843 -0.629565 C -4.033478 -4.684650 -0.486223 C -3.096785 -3.682457 -0.311197 H -3.413868 2.734485 -0.190975 H -5.035448 4.558302 -0.555618 H -4.232159 6.874287 -0.877217 H -1.815133 7.371408 -0.825960 H -0.180971 5.549699 -0.466481 H -0.261805 -5.576415 -0.400470 H -1.953520 -7.354613 -0.708759 H -4.353662 -6.783384 -0.769030 H -5.082894 -4.434635 -0.513142 H -3.403269 -2.653705 -0.202092

S36

Table S27. Summary of calculated maxs for the complexes with several protocols, on geometris optimized ZSC BP86/TZ2P and ZSC COSMO BP86/TZ2P.a

EXPTL UV COSMO/OPT COSMO

LB94 BP86 PBE0 PBE40 LB94 BP86 PBE0 PBE40cisMe 233 242.0 226.0 218.0 221.0 5.12 5.49 5.69 5.61transMe 232 251.0 237.0 210.0 191.0 4.94 5.23 5.90 6.49cisPh 231 315.0 350.0 274.5 250.0 3.94 3.54 4.52 4.96transPh 236 358.0 353.5 288.5 264.0 3.46 3.51 4.30 4.70

UV COSMO/OPT

LB94 BP86 PBE0 PBE40 LB94 BP86 PBE0 PBE40cisMe 233 240.0 274.0 219.0 168.0 5.17 4.52 5.66 7.38transMe 232 245.0 249.0 239.0 188.0 5.06 4.98 5.19 6.59cisPh 231 316.0 312.6 277.0 251.0 3.92 3.97 4.48 4.94transPh 236 356.0 373.4 289.0 265.0 3.48 3.32 4.29 4.68

UV /OPT COSMO UV /OPT UV /OPT COSMO UV /OPT

PBE0 PBE40 PBE0 PBE40 PBE0 PBE40 PBE0 PBE40cisMe 233 232.0 206.6 254.0 206.0 5.34 6.00 4.88 6.02transMe 232 216.0 201.3 216.0 202.0 5.74 6.16 5.74 6.14cisPh 231 249.0 230.0 249.0 251.0 4.98 5.39 4.98 4.94

lmax (nm) lmax (eV)

a UV COSMO = Excitations calculated COSMO F/TZ2P (F=LB94; BP86;PBE0;PBE40); UV = Excitations calculated F/TZ2P (F=LB94; BP86;PBE0;PBE40) without COSMO model; OPT COSMO = Geometries optimized ZSC COSMO BP86/TZ2P; OPT = Geometries optimized ZSC BP86/TZ2P without COSMO model. Acetonitrile has been considered as solvent in the COSMO model.

Table S28. Summary of calculated maxs at for the complexes with several protocols on geometries optimized ZSC B3LYP/TZ2P and ZSC COSMO B3LYP/TZ2P.a

EXPTL UV COSMO/OPT COSMO UV /OPT COSMO

cisMe 233 192.0 6.5 241.00 5.1transMe 232 209.0 5.9 220.00 5.6cisPh 231 268.0 4.6 392.00 3.2transPh 236 246.0 5.0 257.00 4.8

UV COSMO/OPT UV /OPT

cisMe 233 192.0 6.5 241.00 5.1transMe 232 207.0 6.0 220.00 5.6cisPh 231 243.0 5.1 382.00 3.2

lmax (nm) lmax (eV) lmax (nm) lmax (eV)

lmax (nm) lmax (eV) lmax (nm) lmax (eV)

a UV COSMO = Excitations calculated COSMO F/TZ2P (F=LB94; BP86;PBE0;PBE40); UV = Excitations calculated F/TZ2P (F=LB94; BP86;PBE0;PBE40) without COSMO model; OPT COSMO = Geometries optimized ZSC COSMO BP86/TZ2P; OPT = Geometries optimized ZSC BP86/TZ2P without COSMO model. Acetonitrile has been considered as solvent in the COSMO model.

S37

Table S29. Calculated (13C) at NR F/TZ2P// ZSC BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]

Exptl. B3LYP* B3LYP 25 B3LYP 40 PBE15MeCN 116.85 112.66 112.38 114.09 114.09PhCN (CN) 119.2 117.75 116.40 116.64 119.00Cipso 112.8 114.40 113.55 114.35 113.81C2,6 132.5 133.89 133.09 134.06 133.20C3,5 129.5 127.99 126.74 126.99 127.53C4 133.1 131.65 130.92 132.03 131.03Cis-MeCNPt 115.6 109.64 111.77 116.65 110.75Trans-MeCNPt 114.4 117.46 118.63 122.31 118.41Cis-PhCNPt (CN) 115.7 112.07 113.20 116.70 112.91Cipso 109.7 111.66 110.47 110.81 111.05C2,6 133.9 135.06 134.33 135.42 134.39C3,5 129.9 128.41 127.11 127.26 127.95C4 135.6 133.38 132.88 134.28 132.78Trans-PhCNPt (CN) 117.3 119.86 119.92 122.18 120.60Cipso 109.3 110.80 109.67 110.07 110.25C2,6 134.1 135.28 134.59 135.73 134.63

Table S30. Calculated (13C) at ZSC F/TZ2P//ZSC BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]

Exptl. B3LYP* B3LYP 25 B3LYP 40 PBE15 PBE0MeCN 116.85 112.63 112.35 114.07 114.05 114.95PhCN (CN) 119.2 117.72 116.37 116.62 118.96 118.79Cipso 112.8 114.43 113.60 114.40 113.85 113.87C2,6 132.5 133.88 133.08 134.06 133.18 132.38C3,5 129.5 127.98 126.73 126.99 127.52 127.37C4 133.1 131.63 130.91 132.02 131.02 131.35Cis-MeCNPt 115.6 105.58 107.92 113.15 109.89 109.89Trans-MeCNPt 114.4 113.66 114.99 118.88 114.60 116.96Cis-PhCNPt (CN) 115.7 107.86 109.19 113.06 108.61 110.84Cipso 109.7 112.01 110.79 111.07 111.38 111.02C2,6 133.9 135.06 134.34 135.44 134.41 134.71C3,5 129.9 128.40 127.11 127.27 127.93 127.75C4 135.6 133.10 132.65 134.11 132.50 133.10Trans-PhCNPt (CN) 117.3 115.92 116.04 118.42 116.65 117.77Cipso 109.3 110.94 109.84 110.26 110.38 110.12

S38

Table S31. Calculated (13C) at ZSO F/TZ2P//ZSC BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]

Exptl. B3LYP* B3LYP 25 B3LYP 40 PBE15MeCN 116.85 112.79 114.21 114.18 114.21PhCN (CN) 119.2 118.16 118.46 117.02 118.46Cipso 112.8 114.62 113.30 114.59 113.30C2,6 132.5 133.90 132.67 134.06 132.67C3,5 129.5 127.99 126.61 126.98 126.61C4 133.1 131.65 130.59 132.03 130.59Cis-MeCNPt 115.6 105.32 106.24 113.34 106.24Trans-MeCNPt 114.4 109.45 110.43 121.62 110.43Cis-PhCNPt (CN) 115.7 108.45 109.22 112.45 109.22Cipso 109.7 112.44 111.79 111.30 111.79C2,6 133.9 134.74 134.08 135.20 134.08C3,5 129.9 128.22 127.76 127.07 127.76C4 135.6 133.08 132.48 134.09 132.48Trans-PhCNPt 117.3 112.92 113.72 114.36 113.72Cipso 109.3 111.24 110.66 110.29 110.66C2,6 134.1 135.68 135.00 136.15 135.00C3,5 129.9 128.31 127.86 127.09 127.86

Table S32. Calculated (13C) at NR COSMO F/TZ2P//ZSC BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]

Exptl. B3LYP* B3LYP 25 B3LYP 40 PBE15MeCN 116.85 122.41 122.22 124.07 123.67PhCN (CN) 119.2 122.62 121.47 116.64 123.62Cipso 112.8 111.01 110.07 114.35 110.55C2,6 132.5 135.07 134.39 134.06 134.46C3,5 129.5 129.11 127.76 126.99 128.73C4 133.1 134.97 134.26 132.03 134.36Cis-MeCNPt 115.6 117.81 123.73 124.44 118.83Trans-MeCNPt 114.4 126.30 127.58 131.40 127.28Cis-PhCNPt (CN) 115.7 119.90 120.84 124.11 120.54Cipso 109.7 108.45 107.29 107.66 107.91C2,6 133.9 134.80 135.60 136.73 135.64C3,5 129.9 129.41 127.99 127.93 129.04C4 135.6 136.80 136.25 137.58 136.24Trans-PhCNPt 117.3 124.61 124.90 127.44 125.26Cipso 109.3 107.97 106.85 107.27 107.44C2,6 134.1 136.23 135.56 136.70 135.62

S39

Table S33. Calculated (13C) at ZSC COSMO F/TZ2P//ZSC BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]


Table S34. Calculated (13C) at ZSO COSMO F/TZ2P//ZSC BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]

Exptl. B3LYP* B3LYP 25 B3LYP 40 PBE15 PBE0MeCN 116.85 122.48 122.29 114.18 123.74 124.71PhCN (CN) 119.2 122.98 121.81 117.02 123.16 123.92Cipso 112.8 111.23 110.30 114.59 109.95 110.71C2,6 132.5 135.17 134.39 134.06 133.97 134.73C3,5 129.5 129.11 127.75 126.98 127.74 128.49C4 133.1 134.97 134.26 132.03 133.97 134.73Cis-MeCNPt 115.6 111.80 116.64 117.82 112.80 115.46Trans-MeCNPt 114.4 117.43 118.26 121.62 118.47 120.43Cis-PhCNPt (CN) 115.7 114.28 114.92 117.95 114.94 116.55Cipso 109.7 108.96 107.64 107.75 108.38 107.92C2,6 133.9 136.17 135.51 136.75 135.51 135.88C3,5 129.9 129.29 127.86 127.79 128.91 128.63C4 135.6 136.68 136.17 137.58 136.12 136.72Trans-PhCNPt 117.3 112.92 116.80 118.99 117.67 118.60Cipso 109.3 111.24 107.08 107.29 107.73 107.35C2,6 134.1 135.68 135.98 137.18 136.01 136.37C3,5 129.9 128.31 127.91 127.83 128.99 128.70

S40

Table S35. Calculated (13C) at NR F/TZ2P//ZSC COSMO BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]


Table S36. Calculated (13C) at ZSC F/TZ2P//ZSC COSMO BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]


S41

Table S37. Calculated (13C) at ZSO F/TZ2P//ZSC COSMO BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]

Exptl. B3LYP* B3LYP 25 B3LYP 40 PBE15MeCN 116.85 113.30 113.02 114.71 114.70PhCN (CN) 119.2 118.41 117.04 117.23 119.62Cipso 112.8 114.54 113.72 114.52 113.93C2,6 132.5 134.16 133.36 134.31 133.43C3,5 129.5 128.32 127.08 127.32 127.82C4 133.1 131.89 131.16 132.26 131.23Cis-MeCNPt 115.6 103.75 106.08 110.72 105.29Trans-MeCNPt 114.4 110.73 111.32 114.35 111.67Cis-PhCNPt (CN) 115.7 108.16 109.14 112.78 108.94Cipso 109.7 111.92 110.58 110.65 111.29C2,6 133.9 134.77 134.05 135.23 135.10C3,5 129.9 128.51 127.19 127.30 134.10C4 135.6 133.30 132.83 134.28 132.69Trans-PhCNPt 117.3 113.35 112.94 114.73 114.10Cipso 109.3 111.01 109.83 110.05 110.42C2,6 134.1 135.86 135.16 136.32 135.16

Table S38. Calculated (13C) at NR COSMO F/TZ2P//ZSC COSMO BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]


S42

Table S39. Calculated (13C) at ZSC COSMO F/TZ2P//ZSC COSMO BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]


Table S40. Calculated (13C) at ZSO COSMO F/TZ2P//ZSC COSMO BP86/TZ2P level.[ F = B3LYP*; B3LYP25;B3LYP40;PBE15;PBE0;PBE40; CD2Cl2 solvent used in COSMO model]


S43

Figure S13. Orbitals involved in the electronic transitions for cisMe and relevant % weights.Transitions calculated at [ZSC PBE40/TZ2P//ZSC COSMO (ACN) BP86/TZ2P] level

S44

Figure S14. Orbitals involved in the electronic transitions for transMe and relevant % weights. Transitions calculated at [ZSC PBE40/TZ2P//ZSC COSMO (ACN) BP86/TZ2P] level

S45

Figure S15. Orbitals involved in the electronic transitions for cisPh and relevant % weights.Transitions calculated at [ZSC PBE40/TZ2P//ZSC COSMO (ACN) BP86/TZ2P] level.

Figure S16. Orbitals involved in the electronic transitions for transPh and relevant % weights.Transitions calculated at [ZSC PBE40/TZ2P//ZSC COSMO (ACN) BP86/TZ2P] level.

S46

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Pt(II) nitrile complexes: new insights on old complexes … · Web viewPt(II) nitrile complexes: new insights on old complexes from a combined experimental and theoretical study