Efficient PEPPSI-themed palladium N-heterocyclic carbene precatalysts for the mizoroki-heck reaction

Article abstract of DOI:10.1021/om4003297

Two sets of six PEPPSI (pyridine enhanced precatalyst preparation, stabilization, and initiation) themed palladium complexes of amide-functionalized N-heterocyclic carbenes [PdBr₂(NHC)(Py)], where NHC = 1-acetamido-3-R-imidazolin-2-ylidene, 1-acetamido-3-R-benzimidazolin-2- ylidene and Py = pyridine, were prepared. Solid-state structures of all these complexes were determined by single-crystal X-ray diffraction methods. All complexes under scrutiny were found to adopt a trans arrangement with square-planar geometry. These complexes showed excellent catalytic activity toward the Mizoroki-Heck cross-coupling reaction of aryl chlorides and styrene. Benzimidazole-derived complexes exhibited better catalytic activity than imidazole-based complexes. Formation of palladium nanoparticles in the reaction mixture was evidenced by dynamic light scattering and transmission electron microscopy studies and a mercury poisoning experiment, suggesting the possible involvement of palladium nanoparticles in the catalytic reactions.

Full text of DOI:10.1021/om4003297

Supporting Information
Efficient PEPPSI Themed Palladium N-Heterocyclic Carbene Precatalysts for
Mizoroki-Heck Reaction
Yong-Chieh Lin, Hsin-Hsueh Hsueh, Shanker Kanne, Li-Kuang Chang, Fu-Chen Liu*, Ivan J. B.
Lin*
Department of Chemistry, National Dong Hwa University, Hualien 974, Taiwan, ROC
Gene-Hsiang Lee, Shie-Ming Peng
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan, ROC
Table S1. Crystal data and structure refinement for [Pd(Me-imy-CH2CONH2)(Py)Br2] (7)
1pg
1pg
Atomic coordinates ( x 104) and equivalent isotropic displacement parameters
Table S2.
(Å2x 103) for [Pd(Me-imy-CH2CONH2)(Py)Br2] (7)
Anisotropic displacement parameters (Å2x 103) for
Table S3.
1pg
1pg
[Pd(Me-imy-CH2CONH2)(Py)Br2] (7)
Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103)
Table S4.
for [Pd(Me-imy-CH2CONH2)(Py)Br2] (7)
Table S5. Bond lengths [Å] and angles [°] for [Pd(Me-imy-CH2CONH2)(Py)Br2] (7)
Table S6. Crystal data and structure refinement for [Pd(Et-imy-CH2CONH2)(Py)Br2] (8)
2pg
1pg
1pg
Atomic coordinates ( x 104) and equivalent isotropic displacement parameters
Table S7.
(Å2x 103) for [Pd(Et-imy-CH2CONH2)(Py)Br2] (8)
Anisotropic displacement parameters (Å2x 103) for
Table S8.
1pg
1pg
1pg
[Pd(Et-imy-CH2CONH2)(Py)Br2] (8)
Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103)
Table S9.
for [Pd(Et-imy-CH2CONH2)(Py)Br2] (8)
Table S10. Bond lengths [Å] and angles [°] for [Pd(Et-imy-CH2CONH2)(Py)Br2] (8)

Table S11. Crystal data and structure refinement for [Pd(Bu-imy-CH2CONH2)(Py)Br2]
1pg
2pg
(9. 3/2 DMSO)
Atomic coordinates ( x 104) and equivalent isotropic displacement parameters
Table S12.
(Å2x 103) for [Pd(Bu-imy-CH2CONH2)(Py)Br2] (9. 3/2 DMSO)
Anisotropic displacement parameters (Å2x 103) for
Table S13.
2pg
2pg
2pg
[Pd(Bu-imy-CH2CONH2)(Py)Br2] (9. 3/2 DMSO)
Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103)
Table S14.
for [Pd(Bu-imy-CH2CONH2)(Py)Br2] (9. 3/2 DMSO)
Table S15. Bond lengths [Å] and angles [°] for [Pd(Bu-imy-CH2CONH2)(Py)Br2]
(9. 3/2 DMSO)
Table S16. Crystal data and structure refinement for [Pd(Me-bimy-CH2CONH2)(Py)Br2] (10) 1pg
Atomic coordinates ( x 104) and equivalent isotropic displacement parameters
Table S17.
1pg
(Å2x 103) for [Pd(Me-bimy-CH2CONH2)(Py)Br2] (10)
Anisotropic displacement parameters (Å2x 103) for
[Pd(Me-bimy-CH2CONH2)(Py)Br2] (10)
Table S18.
Table S19.
1pg
1pg
Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103)
for [Pd(Me-bimy-CH2CONH2)(Py)Br2] (10)
Table S20. Bond lengths [Å] and angles [°] for [Pd (Me-bimy-CH2CONH2)(Py)Br2] (10)
Table S21. Crystal data and structure refinement for [Pd(Et-bimy-CH2CONH2)(Py)Br2] (11)
1pg
1pg
1pg
Atomic coordinates ( x 104) and equivalent isotropic displacement parameters
Table S22.
(Å2x 103) for [Pd(Et-bimy-CH2CONH2)(Py)Br2] (11)
Anisotropic displacement parameters (Å2x 103) for
Table S23.
1pg
1pg
1pg
[Pd(Et-bimy-CH2CONH2)(Py)Br2] (11)
Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103)
Table S24.
for [Pd(Et-bimy-CH2CONH2)(Py)Br2] (11)
Table S25. Bond lengths [Å] and angles [°] for [Pd(Et-bimy-CH2CONH2)(Py)Br2] (11)
Table S26. Crystal data and structure refinement for [Pd(Bu-bimy-CH2CONH2)(Py)Br2] (12) 1pg
Table S27. 1pg
Atomic coordinates ( x 104) and equivalent isotropic displacement parameters

(Å2x 103) for [Pd(Bu-bimy-CH2CONH2)(Py)Br2] (12)
Anisotropic displacement parameters (Å2x 103) for
[Pd(Bu-bimy-CH2CONH2)(Py)Br2] (12)
Table S28.
Table S29.
1pg
1pg
1pg
Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103)
for [Pd(Bu-bimy-CH2CONH2)(Py)Br2] (12)
Table S30. Bond lengths [Å] and angles [°] for [Pd(Bu-bimy-CH2CONH2)(Py)Br2] (12)

Table S1. Crystal data and structure refinement for [Pd(Me-imy-CH2CONH2)(Py)Br2] (7)
______________________________________________________________________________
Empirical formula
Formula weight
Temperature
C11H14Br2N4OPd
484.48
298(2)K
Wavelength
0.71073A
Crystal system
Space group
Monoclinic
C2/c
Unit cell dimensions
a = 29.9158(15) Å
b = 8.2271(4) Å
c = 14.8484(7) Å
α = 90º.
β = 118.0510(10)º.
γ = 90º.
3
Volume
Z
3225.2(3) Å
8
3
Density (calculated)
1.996 Mg/m
-1
Absorption coefficient
F(000)
6.103 mm
1856
3
Crystal size
Theta range for data collection
Index ranges
0.50 x 0.50 x 0.5 mm
2.59 to 28.33º.
-39<=h<=39,-10<=k<=10,19<=l<=19
Reflections collected
Independent reflections
Completeness to theta=28.33º
Absorption correction
Max. and min. transmission
18218
4012[R(int) = 0.0386]
99.8%
None
0.4612 and 0.1503
2
Refinement method
Data / restraints / parameters
Full-matrix least-squares on F
4012 / 0 / 228
2
Goodness-of-fit on F
1.013
Final R indices [I>2sigma(I)]
R indices (all data)
Largest diff. peak and hole
R1 = 0.0281, wR2 = 0.0650
R1 = 0.0459, wR2 = 0.0724
0.585 and -0.456 e.Å-3
______________________________________________________________________________
a R1 = ΣFo-Fc/ ΣFo.
2
2 2 1/2
b wR2 = {Σw(Fo - Fc2)2/Σw(Fo ) }

Table S2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x
103) for [Pd(Me-imy-CH2CONH2)(Py)Br2] (7)
______________________________________________________________________________
Atom
x
y
z
U(eq)a
______________________________________________________________________________
Pd(1)
Br(1)
Br(2)
C(1)
N(2)
N(1)
C(5)
C(4)
C(6)
N(4)
C(11)
C(7)
C(10)
C(9)
C(8)
O(1)
N(3)
C(3)
C(2)
1213(1)
1297(1)
1173(1)
1648(1)
2157(1)
1504(1)
2475(1)
985(2)
2721(1)
735(1)
251(1)
894(1)
-81(2)
87(2)
581(2)
2794(1)
2864(2)
1924(2)
2327(2)
8267(1)
5859(1)
10734(1)
9414(4)
9353(3)
10404(3)
8471(4)
10858(8)
9578(4)
7051(3)
7495(5)
5768(5)
6681(6)
5371(7)
4914(6)
11015(3)
8862(5)
10953(5)
10311(5)
413(1)
42(1)
54(1)
70(1)
44(1)
46(1)
53(1)
48(1)
77(1)
43(1)
47(1)
59(1)
60(1)
69(1)
73(1)
71(1)
60(1)
65(1)
63(1)
60(1)
-457(1)
1256(1)
-27(2)
409(2)
-835(2)
1334(3)
-1537(4)
2253(2)
863(2)
510(3)
1479(3)
746(3)
1374(3)
1753(3)
2168(2)
3140(3)
-902(3)
-132(3)
______________________________________________________________________________
a
ij
U(eq) is defined as one third of the trace of the orthogonalized U tensor.

Table S3. Anisotropic displacement parameters (Å2x 103) for [Pd(Me-imy-CH2CONH2)(Py)Br2]
(7)
_______________________________________________________________________
11
22
U
33
23
U
13
U
12
U
Atom
U
U
_______________________________________________________________________
Pd(1)
Br(1)
Br(2)
C(1)
N(2)
N(1)
C(5)
C(4)
C(6)
N(4)
C(11)
C(7)
C(10)
C(9)
C(8)
O(1)
N(3)
C(3)
C(2)
38(1)
51(1)
95(1)
44(2)
47(2)
57(2)
42(2)
63(3)
34(1)
38(1)
50(2)
44(2)
45(2)
64(3)
69(3)
72(2)
83(2)
74(3)
59(2)
49(1)
59(1)
56(1)
48(2)
46(1)
59(2)
40(2)
114(4)
43(2)
59(2)
63(2)
84(3)
97(3)
116(4)
94(3)
40(1)
48(2)
67(2)
64(2)
39(1)
52(1)
78(1)
41(2)
46(1)
47(1)
55(2)
54(2)
50(2)
44(1)
69(2)
49(2)
73(3)
50(2)
46(2)
58(1)
55(2)
59(2)
67(2)
0(1)
19(1)
23(1)
55(1)
21(1)
23(1)
29(1)
17(2)
27(2)
18(1)
20(1)
31(2)
19(2)
34(2)
36(2)
23(2)
23(1)
24(2)
41(2)
40(2)
-3(1)
-5(1)
-6(1)
-3(1)
-8(1)
1(1)
1(1)
24(3)
1(1)
-10(1)
-10(1)
0(1)
-4(1)
10(1)
-6(1)
25(3)
-4(1)
-3(1)
-6(2)
13(2)
-20(2)
-15(2)
15(2)
-5(1)
-5(2)
7(2)
-6(1)
5(2)
-2(2)
-3(2)
-32(3)
-18(2)
-8(1)
-10(2)
-9(2)
-17(2)
-8(2)
______________________________________________________________________

Table S4. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for
[Pd(Me-imy-CH2CONH2)(Py)Br2] (7)
______________________________________________________________________________
Atom
x
y
z
U(eq)
______________________________________________________________________________
H(5B)
H(5A)
H(3B)
H(3A)
H(2)
2257(14)
2722(15)
1880(16)
2810(17)
2677(16)
-136(16)
149(17)
3070(18)
-391(18)
1223(16)
880(20)
900(30)
700(17)
757(19)
7620(40)
7990(40)
11620(50)
7920(50)
10400(50)
4870(50)
8410(50)
9400(50)
7070(50)
5390(50)
10470(70)
11810(90)
4080(50)
10560(60)
1400(30)
1230(30)
-1430(30)
3190(30)
110(30)
1560(30)
90(40)
3690(40)
490(30)
1690(30)
-2120(50)
-1430(50)
2140(30)
-1360(40)
61(10)
66(11)
78(13)
72(14)
68(11)
78(12)
82(14)
85(14)
79(13)
70(11)
120(20)
160(30)
80(14)
93(16)
H(9)
H(11A)
H(3C)
H(10)
H(7)
H(4A)
H(4B)
H(8)
H(4C)
______________________________________________________________________________

Table S5. Bond lengths [Å] and angles [°] for [Pd(Me-imy-CH2CONH2)(Py)Br2] (7)
__________________________________________________________________________
Bond lengths
Pd(1)-C(1)
Pd(1)-N(4)
Pd(1)-Br(2)
Pd(1)-Br(1)
C(1)-N(1)
C(1)-N(2)
N(2)-C(2)
N(2)-C(5)
N(1)-C(3)
N(1)-C(4)
C(5)-C(6)
C(5)-H(5B)
C(5)-H(5A)
C(4)-H(4A)
C(4)-H(4B)
C(4)-H(4C)
C(6)-O(1)
1.951(3)
2.095(2)
2.4167(4)
2.4413(4)
1.342(4)
1.348(4)
1.381(4)
1.445(4)
1.384(4)
1.453(5)
1.513(4)
0.99(4)
C(6)-N(3)
N(4)-C(7)
N(4)-C(11)
C(11)-C(10)
C(11)-H(11A)
C(7)-C(8)
C(7)-H(7)
C(10)-C(9)
C(10)-H(10)
C(9)-C(8)
C(9)-H(9)
C(8)-H(8)
N(3)-H(3A)
N(3)-H(3C)
C(3)-C(2)
1.317(4)
1.330(4)
1.338(4)
1.373(6)
0.93(4)
1.376(5)
0.93(4)
1.358(6)
0.88(4)
1.365(6)
0.92(4)
0.85(4)
0.80(4)
0.88(5)
1.319(6)
0.91(4)
0.94(4)
0.91(4)
0.84(6)
0.86(7)
0.88(5)
C(3)-H(3B)
C(2)-H(2)
1.220(4)
Angles
C(1)-Pd(1)-N(4)
C(1)-Pd(1)-Br(2)
N(4)-Pd(1)-Br(2)
C(1)-Pd(1)-Br(1)
N(4)-Pd(1)-Br(1)
Br(2)-Pd(1)-Br(1)
N(1)-C(1)-N(2)
N(1)-C(1)-Pd(1)
N(2)-C(1)-Pd(1)
C(1)-N(2)-C(2)
C(1)-N(2)-C(5)
C(2)-N(2)-C(5)
C(1)-N(1)-C(3)
C(1)-N(1)-C(4)
C(3)-N(1)-C(4)
N(2)-C(5)-C(6)
N(2)-C(5)-H(5B)
C(6)-C(5)-H(5B)
N(2)-C(5)-H(5A)
C(6)-C(5)-H(5A)
H(5B)-C(5)-H(5A)
N(1)-C(4)-H(4A)
N(1)-C(4)-H(4B)
H(4A)-C(4)-H(4B)
N(1)-C(4)-H(4C)
179.01(12)
88.28(9)
91.62(7)
88.03(9)
92.07(7)
176.261(15)
105.5(2)
127.4(2)
127.0(2)
109.9(3)
124.4(3)
125.6(3)
109.9(3)
125.7(3)
124.4(3)
112.3(2)
106(2)
114(2)
107(2)
109(2)
109(3)
114(4)
114(5)
122(6)
116(3)
H(4A)-C(4)-H(4C)
H(4B)-C(4)-H(4C)
O(1)-C(6)-N(3)
O(1)-C(6)-C(5)
N(3)-C(6)-C(5)
C(7)-N(4)-C(11)
C(7)-N(4)-Pd(1)
C(11)-N(4)-Pd(1)
N(4)-C(11)-C(10)
N(4)-C(11)-H(11A)
C(10)-C(11)-H(11A)
N(4)-C(7)-C(8)
N(4)-C(7)-H(7)
C(8)-C(7)-H(7)
C(9)-C(10)-C(11)
C(9)-C(10)-H(10)
C(11)-C(10)-H(10)
C(10)-C(9)-C(8)
C(10)-C(9)-H(9)
C(8)-C(9)-H(9)
C(9)-C(8)-C(7)
104(5)
82(5)
123.2(3)
121.6(3)
115.1(3)
117.1(3)
121.5(2)
121.3(2)
123.2(4)
116(3)
121(3)
122.5(4)
118(2)
119(2)
118.9(4)
124(3)
117(3)
118.7(4)
118(3)
123(3)
119.5(4)
122(3)
119(3)
122(3)
118(3)
C(9)-C(8)-H(8)
C(7)-C(8)-H(8)
C(6)-N(3)-H(3A)
C(6)-N(3)-H(3C)

H(3A)-N(3)-H(3C)
C(2)-C(3)-N(1)
C(2)-C(3)-H(3B)
N(1)-C(3)-H(3B)
119(4)
107.3(3)
133(3)
119(3)
C(3)-C(2)-N(2)
C(3)-C(2)-H(2)
N(2)-C(2)-H(2)
107.3(3)
134(2)
118(2)
___________________________________________________________________________
Symmetry transformations used to generate equivalent atoms:

Table S6. Crystal data and structure refinement for [Pd(Et-imy-CH2CONH2)(Py)Br2] (8)
______________________________________________________________________________
Empirical formula
Formula weight
Temperature
C12H16Br2N4OPd
498.51
150(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Monoclinic
C2/c
Unit cell dimensions
a = 26.8943(18) Å
b = 8.3333(6) Å
c = 16.2697(11) Å
α = 90°.
β = 117.612(2)°.
γ = 90°.
3
Volume
Z
3231.0(4) Å
8
3
Density (calculated)
2.050 Mg/m
-1
Absorption coefficient
F(000)
6.096 mm
1920
3
Crystal size
Theta range for data collection
Index ranges
Reflections collected
Independent reflections
Completeness to theta = 27.50°
Absorption correction
Max. and min. transmission
0.35 x 0.25 x 0.25 mm
1.71 to 27.50°.
-34<=h<=34, -10<=k<=10, -21<=l<=21
12045
3702 [R(int) = 0.0339]
100.0 %
Semi-empirical from equivalents
0.3110 and 0.2242
2
Refinement method
Data / restraints / parameters
Full-matrix least-squares on F
3702 / 2 / 180
2
Goodness-of-fit on F
1.064
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0304, wR2 = 0.0644
R1 = 0.0364, wR2 = 0.0666
-3
Largest diff. peak and hole
1.186 and -0.448 e.Å
______________________________________________________________________________
a R1 = ΣFo-Fc/ ΣFo.
2
2 2 1/2
b wR2 = {Σw(Fo - Fc2)2/Σw(Fo ) } .

Table S7. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x
103) for [Pd(Et-imy-CH2CONH2)(Py)Br2] (8)
__________________________________________________________________________
Atom
x
y
z
U(eq)a
__________________________________________________________________________
Pd
1214(1)
701(1)
1679(1)
786(1)
1477(1)
1261(1)
1157(1)
1297(2)
867(2)
6562(1)
8457(1)
4574(1)
3737(3)
4794(3)
8292(3)
4935(4)
3496(4)
2844(4)
3460(4)
4190(5)
5794(4)
3384(4)
5651(6)
4807(7)
5972(11)
3838(16)
5274(18)
8841(4)
10014(4)
10673(5)
10118(5)
8914(5)
2684(1)
1429(1)
3887(1)
1454(2)
1339(2)
3640(2)
1778(2)
737(2)
19(1)
27(1)
32(1)
24(1)
21(1)
24(1)
20(1)
29(1)
30(1)
31(1)
39(1)
25(1)
28(1)
40(1)
19(1)
32(2)
63(4)
34(4)
29(1)
30(1)
37(1)
39(1)
30(1)
Br(1)
Br(2)
N(1)
N(2)
N(4)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
O(1)
N(3)
C(7)
O(1')
N(3')
C(7')
C(8)
C(9)
C(10)
C(11)
C(12)
807(2)
1693(3)
992(3)
333(2)
-210(2)
1953(1)
2515(2)
2936(2)
2492(2)
2969(4)
2562(7)
2532(6)
791(2)
1507(2)
1875(2)
2581(4)
2011(4)
2231(6)
2461(10)
2124(11)
3640(2)
4230(3)
4845(3)
4863(3)
4254(2)
794(2)
1294(2)
1781(2)
1749(2)
___________________________________________________________________________
a
ij
U(eq) is defined as one third of the trace of the orthogonalized U tensor.

Table S8. Anisotropic displacement parameters (Å2x 103) for [Pd(Et-imy-CH2CONH2)(Py)Br2]
(8)
_________________________________________________________________________
11
22
U
33
23
U
13
U
12
U
Atom
U
U
_________________________________________________________________________
Pd
19(1)
30(1)
32(1)
26(2)
21(1)
27(2)
21(2)
34(2)
36(2)
33(2)
33(2)
25(2)
22(2)
35(2)
47(2)
36(2)
29(2)
22(1)
27(1)
35(1)
25(1)
25(1)
25(1)
22(2)
31(2)
28(2)
36(2)
50(2)
27(2)
33(2)
28(2)
32(2)
42(2)
35(2)
18(1)
24(1)
25(1)
21(1)
20(1)
21(1)
19(2)
23(2)
26(2)
31(2)
39(2)
26(2)
28(2)
32(2)
43(2)
41(2)
30(2)
-2(1)
4(1)
6(1)
-2(1)
0(1)
0(1)
10(1)
12(1)
10(1)
12(1)
11(1)
13(1)
9(1)
14(2)
14(2)
20(2)
21(2)
15(2)
9(2)
1(1)
4(1)
6(1)
-2(1)
4(1)
1(1)
2(1)
5(2)
3(2)
-11(2)
-4(2)
2(1)
1(2)
5(2)
-12(2)
-20(2)
-7(2)
Br(1)
Br(2)
N(1)
N(2)
N(4)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(8)
C(9)
C(10)
C(11)
C(12)
1(1)
-6(1)
-5(1)
-5(2)
-5(2)
0(1)
-3(2)
1(2)
-15(2)
-17(2)
-7(2)
19(2)
28(2)
19(2)
17(2)
___________________________________________________________________________

Table S9. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for
[Pd(Et-imy-CH2CONH2)(Py)Br2] (8)
___________________________________________________________________________
Atom
x
y
z
U(eq)
___________________________________________________________________________
H(2)
H(3)
1452
654
438
3141
1936
3928
2291
5351
3980
3714
6728
6196
6831
6017
5181
6682
3362
3344
8395
10366
11501
10555
8519
350
476
2311
1731
962
1175
381
1891
911
35
36
37
37
59
59
59
30
30
30
30
48
48
75
75
34
36
45
47
36
H(4A)
H(4B)
H(5A)
H(5B)
H(5C)
H(6A)
H(6B)
H(6C)
H(6D)
H(3A)
H(3B)
H(3'A)
H(3'B)
H(8)
282
-162
-503
-318
1964
1919
1897
1937
3265
2902
2890
2255
441
1749
898
2881
2660
2763
2386
3210
4213
5255
5287
4275
H(9)
453
H(10)
H(11)
H(12)
1306
2134
2086
____________________________________________________________________________

Table S10. Bond lengths [Å] and angles [°] for [Pd(Et-imy-CH2CONH2)(Py)Br2] (8)
___________________________________________________________________________
Bond lengths
Pd-C(1)
Pd-N(4)
1.957(3)
2.081(3)
2.4230(4)
2.4410(4)
1.337(4)
1.386(4)
1.457(4)
1.352(4)
1.386(4)
1.443(4)
1.332(4)
1.345(4)
C(2)-C(3)
C(4)-C(5)
C(6)-C(7')
C(6)-C(7)
O(1)-C(7)
N(3)-C(7)
O(1')-C(7')
N(3')-C(7')
C(8)-C(9)
C(9)-C(10)
C(10)-C(11)
C(11)-C(12)
1.331(5)
1.504(5)
1.474(15)
1.533(6)
1.213(7)
1.324(8)
1.251(14)
1.303(15)
1.368(5)
1.366(5)
1.375(6)
1.384(5)
Pd-Br(2)
Pd-Br(1)
N(1)-C(1)
N(1)-C(3)
N(1)-C(4)
N(2)-C(1)
N(2)-C(2)
N(2)-C(6)
N(4)-C(12)
N(4)-C(8)
Angles
C(1)-Pd-N(4)
C(1)-Pd-Br(2)
N(4)-Pd-Br(2)
C(1)-Pd-Br(1)
N(4)-Pd-Br(1)
Br(2)-Pd-Br(1)
C(1)-N(1)-C(3)
C(1)-N(1)-C(4)
C(3)-N(1)-C(4)
C(1)-N(2)-C(2)
C(1)-N(2)-C(6)
C(2)-N(2)-C(6)
C(12)-N(4)-C(8)
C(12)-N(4)-Pd
C(8)-N(4)-Pd
N(1)-C(1)-N(2)
N(1)-C(1)-Pd
N(2)-C(1)-Pd
179.16(12)
88.01(9)
92.33(8)
90.06(9)
89.55(8)
176.737(17)
110.4(3)
125.2(3)
124.2(3)
110.0(3)
125.0(3)
124.9(3)
117.9(3)
121.8(2)
120.2(2)
105.6(3)
126.7(2)
127.7(2)
C(3)-C(2)-N(2)
C(2)-C(3)-N(1)
N(1)-C(4)-C(5)
N(2)-C(6)-C(7')
N(2)-C(6)-C(7)
C(7')-C(6)-C(7)
O(1)-C(7)-N(3)
O(1)-C(7)-C(6)
N(3)-C(7)-C(6)
O(1')-C(7')-N(3')
O(1')-C(7')-C(6)
N(3')-C(7')-C(6)
N(4)-C(8)-C(9)
C(10)-C(9)-C(8)
C(9)-C(10)-C(11)
C(10)-C(11)-C(12)
N(4)-C(12)-C(11)
106.9(3)
107.1(3)
111.7(3)
121.6(6)
109.2(3)
16.0(6)
122.8(5)
122.8(5)
114.3(5)
119.8(14)
126.0(11)
113.4(12)
122.9(3)
119.0(4)
119.0(3)
119.1(4)
122.1(4)
___________________________________________________________________________
Symmetry transformations used to generate equivalent atoms:

Table S11. Crystal data and structure refinement for [Pd(Bu-imy-CH2CONH2)(Py)Br2]
(9.3/2DMSO)
______________________________________________________________________________
Empirical formula
Formula weight
Temperature
C17H29Br2N4O2.50PdS1.50
643.75
200(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Triclinic
P-1
Unit cell dimensions
a = 9.2107(7) Å
b = 14.2729(11) Å
c = 18.7729(14) Å
α = 79.152(2)°.
β = 89.096(2)°.
γ = 86.277(2)°.
3
Volume
Z
2418.7(3) Å
4
3
Density (calculated)
1.768 Mg/m
-1
Absorption coefficient
F(000)
4.222 mm
1276
3
Crystal size
Theta range for data collection
Index ranges
Reflections collected
Independent reflections
Completeness to theta = 27.50°
Absorption correction
Max. and min. transmission
0.30 x 0.20 x 0.04 mm
1.10 to 27.50°.
-11<=h<=11, -18<=k<=18, -24<=l<=24
30026
11076 [R(int) = 0.0646]
99.8 %
Semi-empirical from equivalents
0.8493 and 0.3640
2
Refinement method
Data / restraints / parameters
Full-matrix least-squares on F
11076 / 16 / 500
2
Goodness-of-fit on F
1.107
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0674, wR2 = 0.1488
R1 = 0.1107, wR2 = 0.1685
-3
Largest diff. peak and hole
1.414 and -0.711 e.Å
______________________________________________________________________________
a R1 = ΣFo-Fc/ ΣFo.
2
2 2 1/2
b wR2 = {Σw(Fo - Fc2)2/Σw(Fo ) } .

Table S12. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x
103) for [Pd(Bu-imy-CH2CONH2)(Py)Br2] (9.3/2DMSO)
__________________________________________________________________________
Atom
x
y
z
U(eq)a
__________________________________________________________________________
Pd(1)
Br(1)
Br(2)
O(1)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
C(3)
C(4)
C(5)
7103(1)
8257(1)
5729(1)
3057(6)
4537(7)
4354(7)
5118(7)
9117(7)
5227(9)
383(1)
974(1)
-78(1)
2508(4)
1631(5)
203(5)
3114(5)
-22(5)
8149(1)
9123(1)
7196(1)
7173(3)
8420(3)
8996(4)
6677(4)
7703(4)
8550(4)
8801(5)
9150(5)
9388(8)
9078(8)
9602(9)
9300(11)
9181(15)
8883(15)
9197(18)
9280(20)
7948(4)
7228(4)
7712(5)
7415(6)
7094(6)
7064(6)
7376(5)
1996(1)
2998(1)
989(1)
31(1)
46(1)
49(1)
46(2)
32(1)
43(2)
40(2)
38(2)
35(2)
43(2)
50(2)
45(3)
54(3)
67(4)
86(5)
45(3)
54(3)
67(4)
86(5)
32(2)
34(2)
47(2)
63(3)
60(3)
59(3)
46(2)
35(1)
50(1)
52(1)
46(2)
35(2)
57(2)
44(2)
37(2)
40(2)
45(2)
56(3)
41(3)
49(3)
90(5)
753(6)
1628(6)
736(7)
3222(9)
3109(10)
4820(16)
4214(17)
4520(20)
4230(20)
4470(30)
3390(30)
3450(30)
4920(30)
5083(8)
-772(8)
-1546(9)
-2515(10)
-3345(13)
-850(12)
-1416(16)
-2463(17)
-2940(30)
2469(5)
2682(5)
470(7)
C(6)
C(7)
C(4')
C(5')
C(6')
C(7')
C(8)
C(9)
4324(8)
C(10)
C(11)
C(12)
C(13)
C(14)
Pd(2)
Br(3)
Br(4)
O(2)
N(5)
N(6)
N(7)
N(8)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
10297(9)
11596(10)
11737(10)
10541(10)
9258(9)
8231(1)
9658(1)
6928(1)
12080(6)
10610(7)
10918(9)
9965(7)
231(8)
-566(8)
-1071(7)
-794(6)
4690(1)
3783(1)
5694(1)
6414(4)
6013(5)
4794(5)
6952(5)
4098(5)
5193(6)
6101(7)
5353(7)
3973(8)
3095(9)
2205(13)
2805(3)
1611(4)
1116(5)
3266(4)
2428(4)
1552(5)
1208(5)
899(6)
6306(7)
10030(9)
11883(9)
12063(10)
10563(14)
11435(15)
11340(20)
781(7)
1186(8)
864(12)

C(21)
C(18')
C(19')
C(20')
C(21')
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
S(1)
9960(20)
11080(30)
10090(30)
9760(40)
10990(40)
9978(8)
10780(8)
5064(9)
3773(9)
3728(10)
4988(10)
6237(9)
3348(3)
3995(8)
1874(16)
3738(12)
3602(18)
2570(20)
2060(30)
6701(5)
6661(5)
4622(7)
4250(7)
3262(7)
2707(7)
3140(6)
4598(2)
3621(5)
5014(8)
4444(9)
2129(2)
2998(6)
1350(10)
2401(9)
9180(5)
10153(14)
8540(20)
8620(20)
9102(6)
10083(17)
8710(20)
8610(20)
733(13)
1157(13)
567(13)
610(20)
290(20)
2031(5)
2739(4)
2478(6)
2698(5)
2861(5)
2810(6)
2611(5)
4912(2)
5183(4)
5693(6)
4499(7)
5063(2)
5318(4)
5809(7)
4557(6)
4707(5)
4533(11)
4223(16)
5551(17)
4669(3)
4607(12)
4374(17)
5611(16)
99(6)
41(3)
49(3)
90(5)
99(6)
35(2)
33(2)
54(3)
50(2)
52(2)
55(3)
42(2)
57(1)
64(2)
73(3)
74(3)
59(1)
78(2)
94(5)
77(4)
86(2)
97(6)
94(8)
99(9)
86(2)
115(7)
90(8)
94(9)
O(3)
C(29)
C(30)
S(2)
2635(13)
1702(12)
8680(3)
O(4)
9025(9)
C(31)
C(32)
S(3)
8032(16)
7075(12)
6142(8)
6580(20)
7260(30)
6810(30)
7848(8)
7630(30)
6240(30)
7740(30)
O(5)
C(33)
C(34)
S(3')
O(5')
C(33')
C(34')
___________________________________________________________________________
a
ij
U(eq) is defined as one third of the trace of the orthogonalized U tensor.

Table S13. Anisotropic displacement parameters (Å2x 103) for
[Pd(Bu-imy-CH2CONH2)(Py)Br2] (9.3/2DMSO)
_________________________________________________________________________
11
22
U
33
23
U
13
U
12
U
Atom
U
U
_________________________________________________________________________
Pd(1)
Br(1)
Br(2)
O(1)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
28(1)
45(1)
37(1)
27(3)
31(3)
40(4)
29(3)
31(3)
40(4)
45(5)
39(5)
36(4)
36(4)
39(5)
30(5)
32(5)
50(6)
37(5)
31(1)
33(1)
51(1)
29(3)
29(3)
58(5)
32(4)
32(3)
40(5)
32(4)
45(5)
31(4)
30(4)
43(5)
29(4)
35(5)
49(5)
35(4)
47(1)
74(5)
91(8)
60(7)
28(1)
52(1)
67(1)
54(4)
36(4)
31(4)
41(4)
32(4)
29(4)
35(5)
55(6)
25(4)
24(4)
41(5)
62(7)
65(7)
53(6)
45(5)
30(1)
63(1)
46(1)
53(4)
37(4)
46(5)
58(5)
31(4)
39(5)
48(5)
58(6)
24(4)
31(4)
41(5)
56(6)
59(6)
38(5)
33(5)
62(2)
58(4)
59(7)
76(8)
37(1)
43(1)
49(1)
57(4)
32(4)
52(5)
46(4)
49(4)
35(5)
48(5)
53(6)
36(4)
41(5)
63(6)
99(9)
81(8)
80(8)
60(6)
45(1)
54(1)
54(1)
57(4)
40(4)
76(6)
44(4)
50(4)
43(5)
55(6)
67(7)
52(5)
40(5)
72(7)
57(6)
56(6)
75(7)
54(6)
58(2)
56(4)
68(7)
84(9)
-8(1)
-16(1)
-24(1)
-11(3)
-11(3)
1(3)
4(1)
2(1)
3(1)
-4(3)
-4(3)
17(3)
-6(3)
8(3)
1(1)
-7(1)
-8(1)
-1(3)
3(3)
9(3)
0(3)
-3(3)
-5(4)
6(4)
5(3)
-7(3)
-5(3)
-5(4)
-6(5)
-6(3)
-6(3)
-13(5)
-20(6)
-16(6)
-29(6)
-23(5)
-11(1)
-9(1)
-1(1)
-13(3)
-7(3)
-30(4)
-18(4)
-8(3)
-16(4)
-6(5)
-19(5)
-15(4)
-8(4)
-2(5)
5(5)
4(4)
11(4)
10(4)
-3(3)
-5(4)
10(4)
16(5)
12(5)
9(5)
7(4)
9(1)
-1(1)
8(1)
-8(3)
1(3)
29(4)
-7(3)
7(3)
17(4)
9(4)
26(5)
-2(4)
-1(4)
17(5)
8(4)
C(3)
C(8)
C(9)
4(4)
-1(3)
11(3)
-6(4)
-18(5)
9(5)
2(5)
3(4)
-5(1)
-5(1)
3(1)
C(10)
C(11)
C(12)
C(13)
C(14)
Pd(2)
Br(3)
Br(4)
O(2)
N(5)
N(6)
N(7)
N(8)
C(15)
C(16)
C(17)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
S(1)
2(3)
-5(3)
-15(4)
2(3)
-5(3)
-9(4)
-11(4)
-4(5)
0(3)
-8(3)
4(4)
11(4)
-13(4)
-7(4)
-1(4)
-7(1)
24(4)
25(6)
1(6)
7(5)
-5(5)
0(4)
-2(1)
-10(3)
-21(6)
-7(7)
-1(4)
3(5)
-1(4)
-4(1)
-9(4)
-9(6)
-15(6)
O(3)
C(29)
C(30)

S(2)
59(2)
97(6)
127(12)
79(8)
85(5)
86(5)
66(2)
80(5)
89(9)
84(9)
63(4)
116(6)
52(2)
58(5)
66(8)
69(8)
111(6)
54(4)
-7(1)
-3(4)
4(7)
-5(7)
-20(4)
-17(4)
-4(1)
-31(4)
-12(8)
-15(6)
20(4)
-2(3)
-9(1)
O(4)
C(31)
C(32)
S(3)
-36(5)
-52(9)
-27(7)
-8(3)
S(3')
-2(4)
___________________________________________________________________________

Table S14. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for
[Pd(Bu-imy-CH2CONH2)(Py)Br2] (9.3/2DMSO)
___________________________________________________________________________
Atom
x
y
z
U(eq)
___________________________________________________________________________
H(3A)
H(3B)
H(2)
4730
6029
2545
2321
5896
4513
4666
3152
5559
3925
4453
4832
3198
4435
5452
2405
3547
2981
2877
4851
5498
5398
6140
4937
10228
12402
12643
10592
8436
10360
9036
12511
12838
10830
9508
12469
11087
11871
11885
10104
3290
3223
2158
503
-851
-836
6243
6747
8809
9450
9377
9902
8599
9008
9748
10045
9661
8868
9168
9716
9028
8964
8353
9680
8884
9482
9601
8801
7869
8188
7937
7429
6900
6831
7362
3686
3191
1165
586
48
48
52
60
54
54
64
64
81
H(3)
H(4A)
H(4B)
H(5A)
H(5B)
H(6A)
H(6B)
H(7C)
H(7D)
H(7E)
H(4'A)
H(4'B)
H(5'A)
H(5'B)
H(6'A)
H(6'B)
H(7'A)
H(7'B)
H(7'C)
H(8A)
H(8B)
H(10)
-1573
-1416
-2569
-2517
-3926
-3359
-3310
-1031
-1065
-1141
-1338
-2551
-2784
-3623
-2650
-2876
2357
3029
1014
610
81
128
128
128
54
54
64
64
81
81
128
128
128
39
39
57
75
72
71
55
52
52
54
67
49
49
59
59
H(11)
H(12)
H(13)
H(14)
H(7A)
H(7B)
H(16)
-756
-1608
-1159
6973
7122
6611
5221
4092
3877
3244
2960
2311
1677
1299
H(17)
H(18A)
H(18B)
H(19A)
H(19B)
H(20A)
H(20B)
H(21A)
260
824
1194
1694
396
1189
519
108
108
148

H(21B)
H(21C)
H(18C)
H(18D)
H(19C)
H(19D)
H(20C)
H(20D)
H(21D)
H(21E)
H(21F)
H(22A)
H(22B)
H(24)
9404
9429
10770
12100
10546
9167
9629
8853
10758
11877
11136
8947
10001
5085
2927
2841
4984
7109
2201
1890
3422
1881
1296
1011
8837
7606
7288
6259
6890
7177
7044
7110
8275
6303
7856
6657
6142
5408
6271
8573
7748
6835
2373
1721
3390
3525
3837
3989
2269
2538
1400
2074
2380
6570
7353
5297
4655
2975
2030
2750
4487
5533
5249
4011
5065
4172
1106
816
1692
2503
1870
2983
8739
7858
8654
8901
8710
7936
8932
8973
8012
8787
7910
8854
399
1192
1636
1063
91
596
1127
350
148
148
49
49
59
59
108
108
148
148
148
41
41
64
60
62
302
567
-215
2140
1737
2350
2739
3004
2914
2600
6021
5544
5943
4155
4240
4871
6142
5647
6060
4881
4314
4192
3705
4374
4310
5930
5572
5626
3849
4622
4486
5862
5677
5812
H(25)
H(26)
H(27)
H(28)
66
50
H(29A)
H(29B)
H(29C)
H(30A)
H(30B)
H(30C)
H(31A)
H(31B)
H(31C)
H(32A)
H(32B)
H(32C)
H(33A)
H(33B)
H(33C)
H(34A)
H(34B)
H(34C)
H(33D)
H(33E)
H(33F)
H(34D)
H(34E)
H(34F)
109
109
109
112
112
112
141
141
141
116
116
116
141
141
141
149
149
149
134
134
134
141
141
141
____________________________________________________________________________

Table S15. Bond lengths [Å] and angles [°] for [Pd(Bu-imy-CH2CONH2)(Py)Br2]
(9.3/2DMSO)
___________________________________________________________________________
Bond lengths
Pd(1)-C(1)
Pd(1)-N(4)
Pd(1)-Br(2)
Pd(1)-Br(1)
O(1)-C(9)
N(1)-C(1)
N(1)-C(2)
N(1)-C(8)
N(2)-C(1)
N(2)-C(3)
N(2)-C(4')
N(2)-C(4)
N(3)-C(9)
N(4)-C(10)
N(4)-C(14)
C(2)-C(3)
C(4)-C(5)
C(5)-C(6)
C(6)-C(7)
C(4')-C(5')
C(5')-C(6')
C(6')-C(7')
C(8)-C(9)
C(10)-C(11)
C(11)-C(12)
C(12)-C(13)
C(13)-C(14)
Pd(2)-C(15)
Pd(2)-N(8)
Pd(2)-Br(3)
Pd(2)-Br(4)
O(2)-C(23)
N(5)-C(15)
1.954(8)
2.115(6)
2.4193(11)
2.4379(11)
1.219(9)
N(5)-C(16)
N(5)-C(22)
N(6)-C(15)
N(6)-C(17)
N(6)-C(18)
N(6)-C(18')
N(7)-C(23)
N(8)-C(24)
N(8)-C(28)
C(16)-C(17)
C(18)-C(19)
C(19)-C(20)
C(20)-C(21)
C(18')-C(19')
C(19')-C(20')
C(20')-C(21')
C(22)-C(23)
C(24)-C(25)
C(25)-C(26)
C(26)-C(27)
C(27)-C(28)
S(1)-O(3)
S(1)-C(30)
S(1)-C(29)
S(2)-O(4)
S(2)-C(31)
S(2)-C(32)
S(3)-O(5)
S(3)-C(33)
S(3)-C(34)
S(3')-O(5')
S(3')-C(33')
S(3')-C(34')
1.384(10)
1.459(10)
1.325(10)
1.374(11)
1.487(12)
1.493(16)
1.343(10)
1.337(10)
1.351(10)
1.308(13)
1.524(14)
1.513(15)
1.424(16)
1.496(18)
1.502(19)
1.487(19)
1.521(11)
1.360(12)
1.389(13)
1.375(13)
1.355(12)
1.482(7)
1.758(11)
1.783(11)
1.466(8)
1.740(12)
1.752(11)
1.45(2)
1.349(10)
1.397(10)
1.461(10)
1.333(10)
1.391(10)
1.475(17)
1.487(12)
1.334(10)
1.333(10)
1.356(10)
1.327(12)
1.484(14)
1.552(15)
1.448(16)
1.498(18)
1.497(18)
1.473(19)
1.501(11)
1.363(12)
1.381(14)
1.362(13)
1.380(12)
1.959(8)
2.100(6)
1.70(3)
1.74(3)
1.38(2)
1.75(3)
2.4259(12)
2.4282(12)
1.228(9)
1.342(10)
1.78(3)
Angles
C(1)-Pd(1)-N(4)
C(1)-Pd(1)-Br(2)
N(4)-Pd(1)-Br(2)
C(1)-Pd(1)-Br(1)
N(4)-Pd(1)-Br(1)
Br(2)-Pd(1)-Br(1)
C(1)-N(1)-C(2)
C(1)-N(1)-C(8)
179.2(3)
C(2)-N(1)-C(8)
C(1)-N(2)-C(3)
C(1)-N(2)-C(4')
C(3)-N(2)-C(4')
C(1)-N(2)-C(4)
C(3)-N(2)-C(4)
C(4')-N(2)-C(4)
C(10)-N(4)-C(14)
124.5(7)
86.6(2)
92.68(19)
87.7(2)
93.07(19)
173.59(4)
110.4(7)
125.0(6)
110.3(7)
126.3(13)
122.0(13)
123.1(8)
125.3(9)
21.0(10)
116.6(7)

C(10)-N(4)-Pd(1)
C(14)-N(4)-Pd(1)
N(2)-C(1)-N(1)
N(2)-C(1)-Pd(1)
N(1)-C(1)-Pd(1)
C(3)-C(2)-N(1)
C(2)-C(3)-N(2)
C(5)-C(4)-N(2)
C(4)-C(5)-C(6)
C(7)-C(6)-C(5)
N(2)-C(4')-C(5')
C(6')-C(5')-C(4')
C(7')-C(6')-C(5')
N(1)-C(8)-C(9)
O(1)-C(9)-N(3)
O(1)-C(9)-C(8)
122.5(6)
120.9(5)
105.5(7)
128.1(6)
126.4(6)
106.1(7)
107.6(8)
113.5(10)
109.3(11)
114.3(14)
119.9(18)
116(2)
C(24)-N(8)-C(28)
C(24)-N(8)-Pd(2)
C(28)-N(8)-Pd(2)
N(6)-C(15)-N(5)
N(6)-C(15)-Pd(2)
N(5)-C(15)-Pd(2)
C(17)-C(16)-N(5)
C(16)-C(17)-N(6)
N(6)-C(18)-C(19)
C(20)-C(19)-C(18)
C(21)-C(20)-C(19)
N(6)-C(18')-C(19')
C(18')-C(19')-C(20')
C(21')-C(20')-C(19')
N(5)-C(22)-C(23)
O(2)-C(23)-N(7)
O(2)-C(23)-C(22)
N(7)-C(23)-C(22)
N(8)-C(24)-C(25)
C(24)-C(25)-C(26)
C(27)-C(26)-C(25)
C(28)-C(27)-C(26)
N(8)-C(28)-C(27)
O(3)-S(1)-C(30)
O(3)-S(1)-C(29)
C(30)-S(1)-C(29)
O(4)-S(2)-C(31)
O(4)-S(2)-C(32)
C(31)-S(2)-C(32)
O(5)-S(3)-C(33)
O(5)-S(3)-C(34)
C(33)-S(3)-C(34)
O(5')-S(3')-C(33')
O(5')-S(3')-C(34')
C(33')-S(3')-C(34')
116.3(7)
123.0(6)
120.4(5)
105.5(7)
126.7(6)
127.8(6)
107.6(8)
106.8(8)
107.0(10)
114.5(13)
120.5(17)
102.0(17)
113(2)
115(3)
111.7(6)
123.7(8)
121.4(8)
114.8(7)
123.3(9)
119.7(9)
118.2(9)
119.2(9)
122.8(9)
176.7(3)
88.9(3)
109(3)
112.5(6)
123.6(7)
121.8(7)
114.6(7)
124.3(9)
118.0(8)
118.9(8)
119.0(9)
123.4(8)
105.6(5)
105.6(5)
99.1(6)
106.8(6)
107.1(5)
99.7(6)
105.9(14)
110.2(14)
95.5(15)
106.1(15)
106.4(14)
99.6(14)
N(3)-C(9)-C(8)
N(4)-C(10)-C(11)
C(10)-C(11)-C(12)
C(13)-C(12)-C(11)
C(12)-C(13)-C(14)
N(4)-C(14)-C(13)
C(15)-Pd(2)-N(8)
C(15)-Pd(2)-Br(3)
N(8)-Pd(2)-Br(3)
C(15)-Pd(2)-Br(4)
N(8)-Pd(2)-Br(4)
Br(3)-Pd(2)-Br(4)
C(15)-N(5)-C(16)
C(15)-N(5)-C(22)
C(16)-N(5)-C(22)
C(15)-N(6)-C(17)
C(15)-N(6)-C(18)
C(17)-N(6)-C(18)
C(15)-N(6)-C(18')
C(17)-N(6)-C(18')
C(18)-N(6)-C(18')
91.86(19)
87.6(3)
91.77(19)
175.69(4)
109.3(7)
124.7(6)
126.0(7)
110.8(7)
124.3(8)
123.7(9)
122.3(12)
120.5(12)
33.6(8)
_________________________________________________________________________
Symmetry transformations used to generate equivalent atoms:

Table S16. Crystal data and structure refinement for [Pd(Me-bimy-CH2CONH2)(Py)Br2] (10)
______________________________________________________________________________
Empirical formula
Formula weight
Temperature
C15H16Br2N4OPd
534.54
298(2)K
Wavelength
0.71073 Å
Crystal system
Space group
Triclinic
P-1
Unit cell dimensions
a = 7.6666(3) Å
b = 9.1375(3) Å
c = 13.1036(5) Å
α = 77.8590(10)°.
β = 87.1520(10)°.
γ = 81.7860(10)°.
3
Volume
Z
888.03(6) Å
2
3
Density (Calculated)
1.999 Mg/m
-1
Absorption coefficient
F(000)
5.552 mm
516
3
Crystal size
Theta range for data collection
Index ranges
0.40 x 0.38 x 0.37 mm
1.59 to 28.3°.
-7<=h<=10, -10<=k<=12, -16<=l<=17
Reflections collected
Independent reflections
Completeness to theta = 28.31°
Absorption correction
Max. and min. transmission
5960
4267 [R(int) = 0.0211]
96.4%
None
0.6650 and 0.2148
2
Refinement method
Data / restraints / parameters
Full-matrix least-squares on F
4267 / 0 / 264
2
Goodness-of-fit on F
1.048
Final R indices [I>2sigma(I)]
Rindices(all data)
R1 = 0.0372a, wR2 = 0.1003b
R1 = 0.0461a, wR2 = 0.1063b
-3
Largest diff. peak and hole
0.668 and -0.948 e.Å
______________________________________________________________________________
a R1 = ΣFo-Fc/ ΣFo.
2
2 2 1/2
b wR2 = {Σw(Fo - Fc2)2/Σw(Fo ) }

Table S17. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x
103) for [Pd(Me-bimy-CH2CONH2)(Py)Br2] (10)
______________________________________________________________________________
Atom
x
y
z
U(eq)a
______________________________________________________________________________
Pd(1)
Br(1)
Br(2)
C(1)
N(2)
N(1)
N(4)
C(10)
C(9)
C(7)
C(2)
C(3)
C(8)
11172(1)
13842(1)
8422(1)
9835(4)
9128(4)
9539(4)
12580(4)
7407(4)
9165(5)
8651(5)
8391(4)
7520(5)
10070(8)
8097(6)
7250(6)
13415(6)
12670(7)
7345(4)
14429(7)
14348(7)
13574(7)
6065(4)
6967(6)
9127(1)
7341(1)
10686(1)
7473(4)
7220(3)
6338(3)
10965(4)
8993(4)
8156(5)
5317(4)
5871(4)
5117(5)
6213(7)
3960(5)
3211(5)
11305(5)
11827(5)
9534(4)
13393(5)
12537(6)
13057(6)
9118(4)
3777(5)
1982(1)
2440(1)
1436(1)
2556(3)
3533(2)
2113(2)
1519(2)
4570(3)
4290(3)
2822(3)
3725(3)
4589(4)
1049(4)
2740(4)
3610(5)
600(3)
2200(4)
5341(2)
1074(5)
360(4)
2010(4)
3951(3)
4501(4)
36(1)
52(1)
55(1)
36(1)
36(1)
40(1)
42(1)
37(1)
40(1)
40(1)
38(1)
49(1)
58(1)
53(1)
65(1)
52(1)
57(1)
45(1)
65(1)
66(1)
66(1)
63(1)
60(1)
C(6)
C(5)
C(15)
C(11)
N(3)
C(13)
C(14)
C(12)
O(1)
C(4)
______________________________________________________________________________
a
ij
U(eq) is defined as one third of the trace of the orthogonalized U tensor.

Table S18. Anisotropic displacement parameters (Å2x 103) for
[Pd(Me-bimy-CH2CONH2)(Py)Br2] (10)
_______________________________________________________________________
11
22
U
33
23
U
13
12
U
Atom
U
U
U
_______________________________________________________________________
Pd(1)
Br(1)
Br(2)
C(1)
N(2)
N(1)
N(4)
C(10)
C(9)
C(7)
C(2)
C(3)
C(8)
37(1)
44(1)
48(1)
35(2)
34(1)
45(2)
42(2)
36(2)
35(2)
37(2)
34(2)
43(2)
73(3)
56(2)
58(3)
56(2)
74(3)
36(1)
63(3)
58(3)
86(3)
54(2)
44(2)
30(1)
47(1)
42(1)
31(2)
32(2)
35(2)
38(2)
32(2)
44(2)
30(2)
31(2)
46(2)
57(3)
33(2)
35(2)
55(3)
52(3)
64(2)
45(2)
64(3)
48(3)
72(2)
45(2)
41(1)
64(1)
72(1)
43(2)
43(2)
45(2)
46(2)
42(2)
45(2)
55(2)
47(2)
53(2)
48(2)
73(3)
102(4)
45(2)
47(2)
38(2)
83(4)
65(3)
69(3)
68(2)
80(3)
-9(1)
4(1)
-7(1)
-1(1)
2(1)
-13(1)
-13(1)
-14(2)
-13(1)
-16(1)
-7(1)
-6(1)
-5(1)
6(1)
8(1)
1(1)
1(1)
4(1)
2(2)
-5(1)
-5(1)
-7(1)
-11(1)
-3(1)
-4(2)
-3(1)
-2(1)
-3(2)
-8(3)
-5(2)
-12(2)
-10(2)
-20(2)
14(1)
-23(2)
-16(2)
-26(2)
0(2)
-7(2)
-20(2)
-12(2)
-7(2)
-2(2)
-1(1)
8(2)
-4(2)
-24(2)
-14(2)
-3(2)
-11(2)
-11(2)
-34(2)
5(2)
10(3)
-11(2)
-29(2)
15(2)
3(2)
C(6)
C(5)
-11(2)
-13(3)
7(2)
C(15)
C(11)
N(3)
C(13)
C(14)
C(12)
O(1)
C(4)
0(2)
-2(1)
-12(2)
11(2)
-15(3)
-2(2)
0(2)
-10(2)
_______________________________________________________________________

Table S19. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for
[Pd(Me-bimy-CH2CONH2)(Py)Br2] (10)
______________________________________________________________________________
Atom
x
y
z
U(eq)
______________________________________________________________________________
H(3A)
H(3B)
H(9B)
H(15)
H(4)
6381
8265
10038
9415
5514
5715
4140(30)
70(40)
53
53
10000(50)
13290(60)
6450(70)
8240(70)
7270(60)
10750(80)
12040(80)
9560(70)
15080(70)
6830(50)
13530(80)
9150(80)
15100(80)
10310(120)
8810(50)
10650(50)
3170(60)
3660(60)
5520(50)
5460(70)
11800(70)
7580(60)
14160(60)
2240(50)
13740(70)
6140(70)
12550(70)
7400(110)
40(10)
57(12)
68(14)
74(16)
45(12)
77(18)
90(20)
74(17)
72(15)
51(11)
100(20)
84(19)
94(19)
190(40)
5070(40)
2090(40)
5120(30)
1010(40)
2710(50)
4840(40)
900(40)
3620(30)
2410(50)
760(40)
-230(50)
470(80)
H(6)
H(3)
H(8A)
H(11)
H(9A)
H(13)
H(5)
H(12)
H(8B)
H(14)
H(8C)
______________________________________________________________________________

Table S20. Bond lengths [Å] and angles [°] for [Pd (Me-bimy-CH2CONH2)(Py)Br2] (10)
__________________________________________________________________________
Bond lengths
Pd(1)-C(1)
Pd(1)-N(4)
Pd(1)-Br(2)
Pd(1)-Br(1)
C(1)-N(1)
C(1)-N(2)
N(2)-C(2)
N(2)-C(9)
N(1)-C(7)
N(1)-C(8)
N(4)-C(11)
N(4)-C(15)
C(10)-N(3)
1.946(3)
2.092(3)
2.4185(5)
2.4437(5)
1.341(4)
1.353(4)
1.399(4)
1.444(4)
1.397(5)
1.455(5)
1.319(5)
1.334(5)
1.211(4)
C(10)-O(1)
C(10)-C(9)
C(7)-C(2)
C(7)-C(6)
C(2)-C(3)
C(3)-C(4)
C(6)-C(5)
C(5)-C(4)
C(15)-C(14)
C(11)-C(12)
C(13)-C(14)
C(13)-C(12)
1.319(5)
1.519(5)
1.376(5)
1.393(5)
1.390(5)
1.381(6)
1.384(7)
1.369(8)
1.392(6)
1.376(6)
1.348(8)
1.360(8)
Angles
C(1)-Pd(1)-N(4)
C(1)-Pd(1)-Br(2)
N(4)-Pd(1)-Br(2)
C(1)-Pd(1)-Br(1)
N(4)-Pd(1)-Br(1)
Br(2)-Pd(1)-Br(1)
N(1)-C(1)-N(2)
N(1)-C(1)-Pd(1)
N(2)-C(1)-Pd(1)
C(1)-N(2)-C(2)
C(1)-N(2)-C(9)
C(2)-N(2)-C(9)
C(1)-N(1)-C(7)
C(1)-N(1)-C(8)
C(7)-N(1)-C(8)
C(11)-N(4)-C(15)
C(11)-N(4)-Pd(1)
C(15)-N(4)-Pd(1)
N(3)-C(10)-O(1)
173.99(13)
88.45(10)
91.65(9)
87.42(10)
92.97(9)
173.576(17)
107.4(3)
128.0(3)
124.5(2)
109.8(3)
126.0(3)
124.2(3)
109.8(3)
124.4(4)
125.9(3)
118.0(4)
117.1(3)
124.9(3)
124.1(3)
N(3)-C(10)-C(9)
O(1)-C(10)-C(9)
N(2)-C(9)-C(10)
C(2)-C(7)-C(6)
C(2)-C(7)-N(1)
C(6)-C(7)-N(1)
C(7)-C(2)-C(3)
C(7)-C(2)-N(2)
C(3)-C(2)-N(2)
C(4)-C(3)-C(2)
C(5)-C(6)-C(7)
C(4)-C(5)-C(6)
N(4)-C(15)-C(14)
N(4)-C(11)-C(12)
C(14)-C(13)-C(12)
C(13)-C(14)-C(15)
C(13)-C(12)-C(11)
C(5)-C(4)-C(3)
117.3(3)
118.5(3)
116.4(3)
121.7(4)
106.9(3)
131.4(4)
121.4(3)
106.1(3)
132.5(4)
116.6(4)
116.4(5)
121.8(4)
121.3(4)
123.5(5)
119.6(4)
119.5(5)
118.2(5)
122.2(5)
___________________________________________________________________________
Symmetry transformations used to generate equivalent atoms:

Table S21. Crystal data and structure refinement for [Pd(Et-bimy-CH2CONH2)(Py)Br2] (11)
_______________________________________________________________________
Empirical formula
Formula weight
Temperature
C16H18Br2N4OPd
548.56
150(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Triclinic
P-1
Unit cell dimensions
a = 7.3864(6) Å
b = 9.1748(8) Å
c = 14.2132(12) Å
α = 81.320(2)°.
β = 78.605(2)°.
γ = 84.328(2)°.
3
Volume
Z
931.04(14) Å
2
3
Density (calculated)
1.957 Mg/m
-1
Absorption coefficient
F(000)
5.299 mm
532
3
Crystal size
Theta range for data collection
Index ranges
Reflections collected
Independent reflections
Completeness to theta = 27.50°
Absorption correction
Max. and min. transmission
0.25 x 0.20 x 0.10 mm
1.47 to 27.50°.
-9<=h<=9, -11<=k<=11, -18<=l<=18
10451
4259 [R(int) = 0.0280]
99.7 %
Semi-empirical from equivalents
0.6193 and 0.3509
2
Refinement method
Data / restraints / parameters
Full-matrix least-squares on F
4259 / 0 / 218
2
Goodness-of-fit on F
1.049
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0399, wR2 = 0.0922
R1 = 0.0483, wR2 = 0.0983
-3
Largest diff. peak and hole
2.856 and -0.668 e.Å
_______________________________________________________________________
a R1 = ΣFo-Fc/ ΣFo.
2
2 2 1/2
b wR2 = {Σw(Fo - Fc2)2/Σw(Fo ) }

Table S22. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x
103) for [Pd(Et-bimy-CH2CONH2)(Py)Br2] (11)
______________________________________________________________________________
Atom
x
y
z
U(eq)a
______________________________________________________________________________
Pd
4637(1)
7628(1)
1812(1)
7470(4)
6310(5)
6226(4)
9252(5)
3414(5)
5801(5)
7999(8)
6245(6)
7054(5)
7757(6)
8369(6)
8278(6)
7578(6)
6984(5)
5914(5)
7655(5)
3009(8)
2321(9)
2025(8)
2378(7)
3091(7)
7281(1)
5922(1)
8923(1)
5270(4)
10013(4)
8420(4)
6424(4)
5735(4)
8668(4)
10224(7)
10637(5)
10673(5)
12046(5)
12349(6)
11355(6)
9984(5)
9666(5)
7095(5)
6191(4)
6005(7)
4959(9)
3600(8)
3331(6)
4412(5)
2309(1)
2006(1)
2455(1)
5430(2)
2477(3)
3779(2)
4106(3)
1748(3)
2885(3)
793(4)
1476(3)
3122(3)
3045(4)
3848(4)
4690(4)
4770(3)
3960(3)
4474(3)
4696(3)
862(4)
23(1)
34(1)
34(1)
32(1)
24(1)
22(1)
26(1)
30(1)
23(1)
51(1)
33(1)
27(1)
35(1)
40(1)
38(1)
29(1)
24(1)
25(1)
21(1)
50(1)
66(2)
63(2)
50(2)
37(1)
Br(1)
Br(2)
O(1)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
453(5)
961(5)
1886(5)
2255(4)
____________________________________________________________________________
a
ij
U(eq) is defined as one third of the trace of the orthogonalized U tensor.