Formation of binuclear pyrazolate-bridged palladium carboxylates in the reactions of [Pd(Hdmpz)4](OOCR2) (R = Me, Bu t, Ph) with heterometallic Pd-Co acetate

Article abstract of DOI:10.1134/S0036023609100155

The reactions of [Pd(Hdmpz)₄](OOCR)₂ (R = Me, Bu ^t, Ph, Hdmpz = 3,5-dimethylpyrazole) with the heterometallic acetate Pd(μ-OOCMe)₄Co(NCMe) gives pyrazolate-bridged dimers Pd ₂(μ-dmpz)₂(Hdmp

Full text of DOI:10.1134/S0036023609100155

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2009, Vol. 54, No. 10, pp. 1590–1602. © Pleiades Publishing, Inc., 2009.
Original Russian Text © E.V. Perova, F.M. Miloserdov, M.Ya. Yakovleva, S.E. Nefedov, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 10, pp. 1665–
1677.
COORDINATION COMPOUNDS
Formation of Binuclear Pyrazolate-Bridged Palladium
Carboxylates in the Reactions of [Pd(Hdmpz)4](OOCR2)
(R = Me, But, Ph) with Heterometallic Pd–Co Acetate
E. V. Perova, F. M. Miloserdov, M. Ya. Yakovleva, and S. E. Nefedov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia
Received October 15, 2008
Abstract—The reactions of [Pd(Hdmpz)4](OOCR)2 (R = Me, But, Ph, Hdmpz = 3,5-dimethylpyrazole) with the het-
erometallic acetate Pd(µ-OOCMe)4Co(NCMe) gives pyrazolate-bridged dimers Pd2(µ-dmpz)2(Hdmpz)2(OOCR)2
(R = Me, But, Ph), which were characterized by X-ray diffraction.
DOI: 10.1134/S0036023609100155
The chemistry of complexes containing coordinated
molecules of pyrazole and its analogues attracts
enhanced interest due to the possible deprotonation of
the pyrrole nitrogen atom of the heterocycle to give
pyrazolate bridges and binuclear complexes, which can
be assembled into more complex polynuclear clusters
up to metal-containing polymers combining bridging
unsaturated organic fragments and transition metal
atoms [1–6].
EXPERIMENTAL
All operations on the synthesis and isolation of com-
plexes were carried out under pure argon using anhy-
drous solvents. [Pd(Hdmpz)4](OOCR)2 (R = Me, But,
Ph) and Pd(µ-OOCMe)4Co(NCMe) were synthesized
by reported procedures [7, 12].
IR spectra were recorded on a Specord M-80 spec-
trophotometer in KBr pellets in the frequency range of
392–4000 cm–1.
X-ray diffraction studies were performed by a stan-
dard procedure on a Bruker SMARTApex II automated
diffractometer equipped with a CCD detector (λMo,
graphite monochromator, ω scan mode). The structures
were calculated using the SHELXTL PLUS program
package (PC version) and refined by means of the
SHELXTL-97 package [13, 14]. The crystal data and
refinement details are summarized in Table 1, atomic
coordinates and selected geometric parameters of the
complexes are in Tables 2 to 9.
Synthesis of Pd2(m-dmpz)2(Hdmpz)2(OOCMe)2 (2).
The complex PdCo(OOCMe)4NCMe (0.071 g,
0.16 mmol) in acetonitrile (5 mL) was added to
[Pd(Hdmpz)4](OOCMe)2 (0.1 g, 0.16 mmol) in acetoni-
trile (15 mL) and the mixture was stirred for 15 min at
room temperature. The solution thus formed was con-
centrated to 7 mL and kept for 24 h at –5°C. The pre-
cipitated crystals were separated from the mother
liquor by decantation and dried in an argon flow. Yield,
0.068 g (60%).
The present study deals with the synthesis and struc-
ture of the products of deprotonation reactions of 3,5-
dimethylpyrazole (Hdmpz) coordinated to palla-
dium(II) in the complexes [Pd(Hdmpz)4](OOCR)2) (R =
Me, But, Ph) with the heterometallic lantern dimer
Pd(µ-OOCMe)4Co(NCMe) (1) [7]. The latter corre-
sponds to the recently discovered type of heterometallic
dimers in which the square-planar palladium(II) atom
forms a Chinese lantern structure typical of binuclear
carboxylates irrespective of the nature of attached non-
transition, transition, or rare earth metal [8, 9]. In these
heterometallic dimers, the metal atoms are located at
short nonbonding metal–metal distances, which is
apparently a crucial factor determining the formation of
species with a 1 : 1 Pd–M stoichiometry upon the
reduction with hydrogen under mild conditions (tem-
perature up to 250°ë), as was shown, for example, by
the preparation of the Pd–Zn product from the complex
Pd(µ-OOCMe)4Zn(OH2) [8, 10, 11]. Although the
composition and structure of the intermediates formed
in reduction of palladium(II)-based heterometallic
dimers with hydrogen are unknown, nevertheless, it is
quite obvious that the process involves coordination of
the hydrogen molecule, electron transfer, and removal
of acetic acid molecules.
For Pd2C26H39N9O4 anal. calcd. (%): C, 41.36;
H, 5.23; N, 16.69.
Found (%): C, 41.45; H, 5.38; N, 16.71.
IR (KBr, ν, cm–1): 3424 m br., 3172 w, 3076 w, 3024 w,
2960 m, 2868 w, 2732 w, 1604 s, 1564 s, 1480 m, 1396 s,
1590

FORMATION OF BINUCLEAR PYRAZOLATE-BRIDGED PALLADIUM CARBOXYLATES
1591
Table 1. Crystallographic parameters and structure refinement details for 2–4
2 · MeCN
3 · MeCN
3 · C6H14
4
Molecular formula
C26H39N9O4Pd2
754.46
C32H51N9O4Pd2
838.62
C33H55N8O4Pd2
840.65
C34H40N8O4Pd2
837.54
M
Temperature, K
160(2)
296(2)
120(2)
100(2)
Color
Ligth beige
Triclinic
P-1
Ligth beige
Triclinic
P-1
Ligth beige
Monoclinic
P2(1)/c
Ligth beige
Triclinic
P-1
System
Space group
Unit cell parameters
a, Å
9.5344(7)
10.7589(8)
16.267(1)
6.978(1)
92.918(1)
103.405(1)
1605.8(2)
2
10.059(6)
11.560(7)
18.165(9)
95.02(1)
101.38(1)
104.09(1)
1988(2)
2
12.7140(16)
19.576(3)
16.862(2)
90
8.6137(6)
13.0828(9)
16.5597(12)
81.2300(10)
88.4420(10)
72.3680(10)
1757.3(2)
2
b, Å
c, Å
α, deg
β, deg
γ, deg
V, Å3
Z
108.115(2)
90
3988.8(9)
4
ρ
calcd, mg/m3
1.560
1.401
1.400
1.583
µ, mm–1
1.164
0.948
0.945
1.072
F(000)
764
860
1732
848
Crystal dimensions, mm
Scanning θ range, deg
Index ranges
0.10 × 0.08 × 0.06 0.14 × 0.12 × 0.10 0.14 × 0.12 × 0.10 0.16 × 0.14 × 0.12
1.96 –28.00
1.84–25.00
1.69–26.00
2.21–27.00
–12 ≤ h ≤ 12,
–14 ≤ k ≤ 14,
–21 ≤ l ≤ 21
–11 ≤ h ≤ 11,
–13 ≤ k ≤ 13,
–20 ≤ l ≤ 21
–15 ≤ h ≤ 15,
–24 ≤ k ≤ 24,
–20 ≤ l ≤ 20
–11 ≤ h ≤ 10,
–16 ≤ k ≤ 16,
–21 ≤ l ≤ 21
Number of reflections
Number of unique reflections
GOOF
16576
12097
26983
16666
7702 [R(int) = 0.0548] 6896 [R(int) = 0.1025] 7721 [R(int) = 0.0762] 7602 [R(int) = 0.0413]
0.998
0.995
1.169
1.018
R [I > 2σ(I)]
R1 = 0.0299,
wR2 = 0.0620
R1 = 0.0597,
wR2 = 0.1539
R1 = 0.0541,
wR2 = 0.1358
R1 = 0.0345,
wR2 = 0.0815
R (for all reflections)
R1 = 0.0399,
wR2 = 0.0648
R1 = 0.0925,
wR2 = 0.1737
R1 = 0.1189,
wR2 = 0.1842
R1 = 0.0486,
wR2 = 0.0884
Electron density peaks (min/max), 1.052 and –0.460
e Å–3
1.268 and –1.360
1.670 and –0.652
1.620 and –0.682
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 10 2009

1592
PEROVA et al.
Table 2. Atomic coordinates (×104) and equivalent isotropic
factors (Å2, ×103) for complex 2
1348 s, 1308 m, 1260 s, 1220 s, 1176 w, 1152 w, 1092 s,
1028 s, 800 s, 640 w, 612 w, 480 w, 384 m, 312 w.
Synthesis of Pd2(m-dmpz)2(Hdmpz)2(OOCBut)2 (3).
Atom
x
y
z
Ueq
The complex [Pd(Hdmpz)4](OOCBut)2 (0.1 g,
0.14 mmol) was dissolved in acetonitrile (10 mL). A
solution of PdCo(OOCMe)4NCMe (0.062 g,
0.14 mmol) in acetonitrile (5 mL) was added to the
resulting solution. The reaction mixture was stirred for
30 min at room temperature, concentrated to 7 mL, and
kept for 24 h at –5°C. The precipitated crystals were
separated from the mother liquor by decantation and
dried in an argon flow. Yield, 0.073 g (65%)
Pd(1)
Pd(2)
O(1)
O(2)
O(3)
O(4)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
N(9)
C(1)
8583(1)
7723(1)
1561(1)
2573(1)
1475(1)
2380(2)
3671(1)
3891(1)
1602(1)
2003(1)
1060(1)
1486(1)
2144(1)
2927(1)
3142(1)
3061(1)
5371(2)
1301(2)
823(2)
21(1)
21(1)
31(1)
56(1)
30(1)
37(1)
23(1)
24(1)
22(1)
22(1)
25(1)
28(1)
25(1)
27(1)
78(1)
29(1)
42(1)
33(1)
30(1)
43(1)
26(1)
37(1)
27(1)
26(1)
35(1)
29(1)
41(1)
33(1)
32(1)
47(1)
31(1)
45(1)
38(1)
33(1)
48(1)
34(1)
58(1)
29(1)
42(1)
63(1)
91(2)
9976(1) 10583(1)
9692(2)
6337(2)
7432(2)
11512(3)
9252(2) 11145(2)
8460(2)
7396(2)
9098(2)
9038(2)
For Pd2C32H51N9O4 anal calcd. (%): C, 45.85; H,
6.10; N, 15.66.
8003(2) 10242(2)
10137(2) 8900(2)
10719(2) 10100(2)
Found (%): C, 45.76; H, 6.08; N, 15.03.
IR (KBr, ν, cm–1): 3424 m br., 3175 w, 3080 m,
3020 m, 2960 m, 2732 w, 1602 s, 1564 s, 1483 m,
1391 s, 1344 s, 1302 m, 1265 s, 1219 s, 1178 w, 1093 s,
1027 s, 800 s, 640 w, 480 w, 384 m, 312 w.
Synthesis of Pd2(m-dmpz)2(Hdmpz)2(OOCPh)2 (4).
A solution of PdCo(OOCMe)4NCMe (0.062 g, 0.14 mmol)
in acetonitrile (5 mL) was added to a solution of
[Pd(Hdmpz)4](OOCPh)2 (0.1 g, 0.14 mmol) in acetoni-
trile (10 mL). The resulting solution was stirred for 30 min
at room temperature, concentrated to 5 mL, and kept for
24 h at –5°C. The precipitated crystals were separated
from the mother liquor by decantation and dried in an
argon flow. Yield, 0.088 g (75%)
7082(2)
6817(2)
6580(2)
6981(2)
11964(2) 10866(2)
12691(2) 9924(2)
12272(4) 15777(3)
6042(3)
5064(3)
9004(3)
7815(3)
C(2)
C(3)
5793(3) 10212(3)
7046(3) 10972(3)
7404(3) 12346(3)
1508(2)
1958(2)
2357(2)
390(1)
C(4)
C(5)
C(6)
10877(3)
10507(3)
11950(3)
8739(2)
7537(3)
9858(2)
For Pd2C34H40N8O4 anal calcd. (%): C, 48.79; H,
4.78; N, 13.35.
C(7)
–214(2)
386(2)
C(8)
Found (%): C, 48.71; H, 4.91; N, 13.38.
C(9)
11823(3) 10690(2)
12692(3) 12027(3)
1082(2)
1398(2)
1926(2)
1085(2)
2588(2)
3216(2)
4077(2)
3590(2)
3794(2)
3790(2)
3454(2)
3484(2)
1879(2)
1708(2)
4104(2)
4943(2)
5763(2)
6251(3)
IR (KBr, ν, cm–1): 3430 m br., 3177 w, 3085 m,
3028 m, 2925 m, 2782 w, 1608 s, 1569 s, 1420 m, 1362
s, 1303 m, 1173 m, 1065 m, 1025 m, 814 m, 758 w,
715 s, 685 m, 591 w, 517 w, 455 w.
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
6238(3)
6247(3)
5418(3)
5819(3)
5361(4)
5396(2)
4676(3)
5048(3)
6075(3)
6289(3)
RESULTS AND DISCUSSION
Previously, it was found that the heterometallic dimer
Pd(µ-OOCMe)4Co(NCMe) (1)) containing a labile aceto-
nitrile molecule reacts with bidentate N-donors (phenan-
throline or bipyridine) to give complexes in which the
ligand is bound to the added metal atom and the three-
bridged binuclear fragment is retained [15]. Unlike
bidentate donors, monodentate pyridine destroys the
binuclear complex yielding the pentanuclear complex
{[Pd(µ-OOCMe)4]Co}2(OOCMe)2Pdpy2, which was also
obtained in a quantitative yield by an independent syn-
thetic route starting from mononuclear Pd(py)2(OOCMe)2
and 1 [16].
12857(3) 11892(3)
12385(3) 13116(3)
14172(3) 11588(3)
14029(3) 10327(3)
14994(3)
10914(3)
11623(4)
9429(3)
6495(3)
5379(3)
8677(3) 10279(3)
8271(3) 10791(3)
11512(5) 15155(4)
10525(5) 14338(5)
It was expected that complex 1 would react with com-
pounds (PdL4)2+(OOCR–)2 containing an outer-sphere
two-electron carboxylate anion to give the anions Pd(µ-
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 10 2009

FORMATION OF BINUCLEAR PYRAZOLATE-BRIDGED PALLADIUM CARBOXYLATES
1593
Table 3. Bond lengths (d) and bond angles (ω) for complex 2
Bond
d, Å
Bond
d, Å
Angle
ω, deg
Angle
ω, deg
61.55(6)
Pd(1)–N(3)
Pd(1)–O(1)
Pd(1)–Pd(2)
Pd(2)–N(4)
Pd(2)–O(3)
O(2)–C(21)
O(4)–C(23)
N(1)–N(2)
N(3)–C(6)
1.9919(19) Pd(1)–N(1)
2.0145(17) Pd(1)–N(5)
2.0044(19) N(2)Pd(2)Pd(1)
2.0158(19) N(7)Pd(2)Pd(1)
61.79(6)
N(4)Pd(2)Pd(1)
116.35(6)
O(3)Pd(2)Pd(1) 120.51(5)
3.2549(3)
Pd(2)–N(2)
1.988(2)
2.007(2)
1.273(3)
1.275(3)
1.348(3)
1.340(3)
1.366(3)
1.335(3)
1.343(3)
1.351(3)
1.143(5)
1.498(4)
1.494(4)
1.486(4)
1.498(4)
1.490(4)
1.495(4)
1.494(4)
1.484(4)
1.513(4)
C(21)O(1)Pd(1) 121.51(17) C(23)O(3)Pd(2) 118.34(16)
1.9935(19) Pd(2)–N(7)
2.0216(16) O(1)–C(21)
C(1)N(1)N(2)
N(2)N(1)Pd(1)
C(4)N(2)Pd(2)
C(6)N(3)N(4)
N(4)N(3)Pd(1)
C(9)N(4)Pd(2)
C(11)N(5)N(6)
N(6)N(5)Pd(1)
C(16)N(7)N(8)
N(8)N(7)Pd(2)
N(1)C(1)C(3)
C(3)C(1)C(2)
N(2)C(4)C(3)
C(3)C(4)C(5)
N(3)C(6)C(7)
C(6)C(8)C(9)
N(4)C(9)C(10)
108.6(2)
C(1)N(1)Pd(1)
133.26(18)
109.0(2)
118.11(14) C(4)N(2)N(1)
132.37(18) N(1)N(2)Pd(2)
108.59(19) C(6)N(3)Pd(1)
117.96(14) C(9)N(4)N(3)
132.64(17) N(3)N(4)Pd(2)
1.221(3)
1.242(3)
1.359(3)
1.344(3)
1.344(3)
1.350(3)
1.335(3)
1.349(3)
1.379(4)
1.395(4)
1.388(3)
1.385(3)
1.400(4)
1.379(4)
1.399(4)
1.373(4)
1.514(4)
1.467(6)
O(3)–C(23)
N(1)–C(1)
N(2)–C(4)
N(3)–N(4)
N(5)–C(11)
N(6)–C(14)
N(7)–N(8)
N(9)–C(25)
C(1)–C(2)
118.55(14)
133.16(17)
108.47(19)
118.61(14)
N(4)–C(9)
107.0(2)
119.87(15) C(14)N(6)N(5)
106.6(2) C(16)N(7)Pd(2) 132.71(18)
120.56(15) C(19)N(8)N(7)
C(11)N(5)Pd(1) 133.06(17)
N(5)–N(6)
N(7)–C(16)
N(8)–C(19)
C(1)–C(3)
111.1(2)
111.3(2)
122.6(2)
106.6(2)
121.2(2)
108.2(2)
129.6(2)
108.3(2)
130.2(2)
108.0(2)
129.4(2)
107.7(2)
131.1(2)
122.3(2)
106.4(2)
121.5(2)
N(1)C(1)C(2)
C(1)C(3)C(4)
N(2)C(4)C(5)
N(3)C(6)C(8)
C(8)C(6)C(7)
N(4)C(9)C(8)
C(8)C(9)C(10)
C(3)–C(4)
C(4)–C(5)
C(6)–C(8)
C(6)–C(7)
C(8)–C(9)
C(9)–C(10)
C(11)–C(12)
C(14)–C(15)
C(16)–C(17)
C(19)–C(20)
C(23)–C(24)
C(11)–C(13)
C(13)–C(14)
C(16)–C(18)
C(18)–C(19)
C(21)–C(22)
C(25)–C(26)
N(5)C(11)C(13) 108.9(2)
C(13)C(11)C(12) 130.2(2)
N(6)C(14)C(13) 106.7(2)
N(5)C(11)C(12) 120.9(2)
C(14)C(13)C(11) 106.3(2)
N(6)C(14)C(15) 121.0(2)
Angle
ω, deg
Angle
ω, deg
C(13)C(14)C(15) 132.3(2)
N(7)C(16)C(18) 109.1(2)
N(3)Pd(1)N(1)
N(1)Pd(1)O(1)
N(1)Pd(1)N(5)
N(3)Pd(1)Pd(2)
90.21(8) N(3)Pd(1)O(1)
91.12(7) N(7)C(16)C(17) 120.4(2)
C(18)C(16)C(17) 130.4(3)
N(8)C(19)C(18) 106.4(2)
C(18)C(19)C(20) 133.0(3)
O(2)C(21)C(22) 119.7(3)
176.84(8) N(3)Pd(1)N(5) 176.18(8) C(19)C(18)C(16) 106.6(2)
90.04(8) O(1)Pd(1)N(5)
61.88(6) N(1)Pd(1)Pd(2)
88.82(8) N(8)C(19)C(20) 120.6(3)
61.47(6) O(2)C(21)O(1) 126.0(3)
O(1)Pd(1)Pd(2) 121.66(5) N(5)Pd(1)Pd(2) 115.04(6) O(1)C(21)C(22) 114.3(3)
O(4)C(23)O(3)
125.3(2)
N(2)Pd(2)N(4)
N(4)Pd(2)N(7)
N(4)Pd(2)O(3)
89.13(8) N(2)Pd(2)N(7) 178.12(8) O(4)C(23)C(24) 120.0(2)
O(3)C(23)C(24) 114.7(2)
90.16(8) N(2)Pd(2)O(3)
177.80(7) N(7)Pd(2)O(3)
91.31(8) N(9)C(25)C(26) 178.8(5)
89.47(8)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 10 2009

1594
PEROVA et al.
Table 4. Atomic coordinates (×104) and equivalent isotropic factors (Å2, ×103) for complex 3 · MeCN
Atom
x
y
z
Ueq
Atom
C(10)
x
y
z
Ueq
93(3)
4241(11) 10038(8)
8896(9) 8584(7)
8432(10) 9608(8)
1797(6)
973(4)
643(6)
884(5)
1337(5)
1476(6)
3115(6)
Pd(1)
Pd(2)
6627(1)
5834(1)
8259(1)
6486(1)
1934(1)
3170(1)
44(1)
49(1)
57(2)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
O(1)
O(2)
O(3)
O(4)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
N(9)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
5407(5)
4206(7)
6920(6)
8101(8)
7589(6)
7897(6)
4704(7)
5026(6)
8220(7)
8902(6)
4113(7)
3497(6)
7989(5)
6168(5)
5295(5)
5496(6)
7843(5)
8600(5)
7659(5)
8405(5)
8025(5)
7188(5)
5055(5)
4806(5)
880(3)
969(3)
57(1)
79(2)
63(1)
94(2)
49(2)
49(2)
55(2)
49(2)
50(2)
51(2)
55(2)
53(2)
145(4)
65(2)
93(3)
70(2)
55(2)
78(3)
68(2)
101(4)
79(3)
65(2)
89(3)
9981(9)
9965(8)
8098(8)
7204(7)
67(2)
3468(3)
2556(4)
3493(3)
2961(3)
2926(4)
2408(3)
1471(3)
1691(3)
2788(4)
2046(4)
56(2)
10887(10) 6361(8)
3553(10) 4108(8)
87(3)
75(3)
4027(12) 4128(11) 3957(6)
110(4)
90(3)
2584(11) 3301(8)
2521(9) 3724(7)
1647(11) 3233(9)
4490(8) 6996(7)
3802(10) 6885(9)
2571(7)
1886(6)
1111(6)
606(4)
71(3)
100(4)
50(2)
–233(5)
77(2)
3245(12) 7950(10) –387(6)
2604(13) 5737(11) –483(6)
4873(11) 6827(11) –684(6)
104(3)
122(4)
101(3)
63(1)
6627(14) 10411(11) 4240(7)
8644(10) 8161(7)
8577(12) 7529(9)
4110(5)
4798(5)
3993(5)
3273(5)
2856(6)
3186(5)
7774(9)
5028(7)
3100(5)
9671(9)
9192(8)
9133(8)
9365(6)
8366(15) 4002(12) 3331(10)
7440(16) 2829(12) 2902(9)
8252(15) 3788(13) 4161(9)
9759(16) 4217(14) 3373(10)
6460(20) 9553(17) 4888(12)
6160(20) 8954(16) 5461(11)
134(4)
157(5)
155(5)
174(5)
168(7)
176(7)
9868(9) 10314(8)
3623(9) 7907(8)
3022(11) 7235(10) 3761(7)
3263(9)
4167(9)
8808(8)
9124(7)
2818(6)
2347(5)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 10 2009

FORMATION OF BINUCLEAR PYRAZOLATE-BRIDGED PALLADIUM CARBOXYLATES
1595
Table 5. Bond lengths (d) and bond angles (ω) for complex 3 · MeCN
Bond
d, Å
Bond
d, Å
Angle
ω, deg
121.57(16) N(7)Pd(2)Pd(1) 115.79(18)
C(26)O(3)Pd(2) 122.4(5)
Angle
ω, deg
Pd(1)–N(2)
Pd(1)–O(1)
Pd(1)–Pd(2)
Pd(2)–N(1)
Pd(2)–N(7)
O(2)–C(21)
O(4)–C(26)
N(1)–N(2)
N(3)–C(6)
1.988(6)
2.013(5)
Pd(1)–N(4)
Pd(1)–N(5)
2.005(6)
2.013(6)
1.996(6)
2.002(5)
1.273(9)
O(3)Pd(2)Pd(1)
C(21)O(1)Pd(1) 121.9(5)
3.2547(15) Pd(2)–N(3)
C(1)N(1)N(2)
N(2)N(1)Pd(2)
C(4)N(2)Pd(1)
109.1(6)
116.7(4)
134.0(5)
108.6(7)
118.8(5)
133.7(6)
105.7(6)
120.1(4)
107.1(7)
C(1)N(1)Pd(2)
C(4)N(2)N(1)
N(1)N(2)Pd(1)
C(6)N(3)Pd(2)
C(9)N(4)N(3)
N(3)N(4)Pd(1)
134.0(5)
106.2(6)
119.1(4)
132.6(6)
108.7(6)
117.6(4)
2.000(6)
2.036(6)
1.219(9)
1.230(10)
1.389(8)
1.348(10)
1.333(9)
1.360(8)
1.341(8)
1.356(10)
1.392(12)
1.374(11)
1.369(13)
1.376(13)
1.373(11)
1.376(12)
1.346(13)
1.372(13)
1.526(11)
1.498(12)
1.507(13)
1.493(19)
1.34(3)
Pd(2)–O(3)
O(1)–C(21)
O(3)–C(26)
N(1)–C(1)
1.264(10) C(6)N(3)N(4)
1.337(10) N(4)N(3)Pd(2)
N(2)–C(4)
1.364(9)
1.364(8)
1.351(9)
1.349(9)
C(9)N(4)Pd(1)
C(11)N(5)N(6)
N(6)N(5)Pd(1)
N(8)N(7)C(16)
N(3)–N(4)
C(11)N(5)Pd(1) 134.1(5)
C(14)N(6)N(5) 110.9(6)
N(4)–C(9)
N(5)–C(11)
N(6)–C(14)
N(7)–C(16)
N(9)–C(31)
C(1)–C(2)
N(5)–N(6)
N(7)–N(8)
N(8)–C(19)
C(1)–C(3)
N(8)N(7)Pd(2)
119.8(4)
1.347(10) C(16)N(7)Pd(2) 131.9(6)
N(7)N(8)C(19) 111.0(7)
1.61(2)
N(1)C(1)C(3)
108.8(7)
130.0(8)
109.8(7)
129.0(8)
121.5(9)
108.0(8)
121.2(8)
N(1)C(1)C(2)
C(4)C(3)C(1)
N(2)C(4)C(5)
N(3)C(6)C(8)
C(8)C(6)C(7)
N(4)C(9)C(8)
C(8)C(9)C(10)
121.1(8)
106.0(7)
121.2(7)
107.1(8)
131.4(9)
107.6(8)
131.1(8)
1.506(12) C(3)C(1)C(2)
1.493(11) N(2)C(4)C(3)
1.491(13) C(3)C(4)C(5)
1.515(13) N(3)C(6)C(7)
1.504(11) C(6)C(8)C(9)
1.505(11) N(4)C(9)C(10)
C(3)–C(4)
C(4)–C(5)
C(6)–C(8)
C(6)–C(7)
C(8)–C(9)
C(9)–C(10)
C(11)–C(12)
C(14)–C(15)
C(16)–C(17)
C(19)–C(20)
C(22)–C(25)
C(22)–C(24)
C(27)–C(30)
C(27)–C(29)
C(11)–C(13)
C(13)–C(14)
C(16)–C(18)
C(18)–C(19)
C(21)–C(22)
C(22)–C(23)
C(26)–C(27)
C(27)–C(28)
C(31)–C(32)
1.506(13) N(5)C(11)C(13) 109.8(7)
1.485(13) C(13)C(11)C(12) 130.9(8)
1.485(13) N(6)C(14)C(13) 106.6(7)
1.523(14) C(13)C(14)C(15) 131.5(8)
1.348(17) C(18)C(16)C(17) 132.5(9)
N(5)C(11)C(12) 119.2(8)
C(11)C(13)C(14) 106.9(8)
N(6)C(14)C(15) 121.9(8)
C(18)C(16)N(7) 107.8(8)
N(7)C(16)C(17) 119.7(9)
N(8)C(19)C(18) 104.3(8)
C(18)C(19)C(20) 133.0(9)
1.57(2)
C(16)C(18)C(19) 109.8(8)
N(8)C(19)C(20) 122.7(9)
Angle
ω, deg
Angle
ω, deg
O(2)C(21)O(1)
123.5(7)
O(2)C(21)C(22) 121.5(8)
N(2)Pd(1)N(4)
N(4)Pd(1)O(1)
89.5(2)
92.1(2)
N(2)Pd(1)O(1) 177.0(2)
O(1)C(21)C(22) 114.9(7)
C(25)C(22)C(24) 108.2(9)
C(25)C(22)C(21) 108.8(8)
C(25)C(22)C(23) 109.3(9)
C(23)C(22)C(24) 109.3(9)
C(23)C(22)C(21) 110.4(7)
O(4)C(26)O(3) 125.5(8)
N(2)Pd(1)N(5)
O(1)Pd(1)N(5)
90.0(2)
88.6(2)
N(4)Pd(1)N(5) 177.1(2)
N(2)Pd(1)Pd(2) 61.77(17) N(4)Pd(1)Pd(2) 61.93(17) C(24)C(22)C(21) 110.9(8)
O(1)Pd(1)Pd(2) 121.22(14) N(5)Pd(1)Pd(2) 115.37(16) O(4)C(26)C(27) 118.2(10) O(3)C(26)C(27) 116.2(9)
N(3)Pd(2)N(1)
N(1)Pd(2)O(3)
90.1(3)
90.9(2)
N(3)Pd(2)O(3) 176.7(2)
C(30)C(27)C(28) 117.4(15) C(30)C(27)C(26) 113.6(12)
C(28)C(27)C(26) 110.6(12) C(30)C(27)C(29) 102.6(14)
C(28)C(27)C(29) 100.0(12) C(26)C(27)C(29) 111.3(12)
N(3)Pd(2)N(7)
O(3)Pd(2)N(7)
92.0(3)
87.2(2)
N(1)Pd(2)N(7) 176.0(2)
N(3)Pd(2)Pd(1) 61.67(19) N(1)Pd(2)Pd(1) 62.44(17)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 10 2009

1596
PEROVA et al.
Table 6. Atomic coordinates (×104) and equivalent isotropic factors (Å2, ×103) for complex 3 · C6H14
Atom
Pd(1)
x
y
z
Ueq
Atom
C(11)
x
y
z
Ueq
4428(1)
6973(1)
3590(4)
5075(5)
8241(4)
7269(5)
4707(5)
5775(5)
5171(5)
6219(5)
4226(5)
5112(5)
7669(5)
7128(6)
4059(6)
2826(6)
4704(7)
5780(7)
6839(8)
4833(6)
3719(7)
5697(7)
6549(7)
7688(8)
6661(1)
6668(1)
7529(3)
8172(3)
6378(3)
6322(4)
6935(3)
6932(3)
5773(3)
5773(3)
6388(3)
6253(3)
7596(3)
8146(3)
7115(4)
7155(5)
7226(4)
7109(4)
7153(5)
5123(4)
4952(5)
4704(4)
5121(4)
4960(5)
6165(1)
6140(1)
6192(3)
6519(5)
7133(3)
8009(4)
5113(4)
5100(4)
6123(3)
6098(4)
7257(4)
7928(4)
6236(4)
6384(4)
4347(5)
4153(5)
3851(5)
4331(5)
4125(6)
6112(4)
6152(6)
6078(5)
6070(5)
6059(6)
39(1)
43(1)
50(1)
97(3)
55(1)
85(2)
43(2)
44(2)
39(1)
48(2)
45(2)
48(2)
51(2)
57(2)
46(2)
63(2)
50(2)
51(2)
76(3)
47(2)
68(2)
59(2)
51(2)
82(3)
3338(6)
2210(6)
3670(7)
4808(7)
5648(9)
8668(6)
9505(7)
8727(7)
7749(8)
7307(9)
4082(7)
3338(8)
4018(9)
2835(9)
6307(4)
6415(5)
6123(4)
6092(4)
5969(5)
7826(5)
7352(5)
8517(5)
8718(5)
9387(5)
8086(4)
8719(5)
9319(5)
8913(5)
7508(5)
6935(6)
8334(5)
8592(5)
9424(6)
6269(6)
6121(7)
6418(7)
6495(6)
6672(8)
6356(5)
6324(6)
6781(7)
5411(6)
6730(8)
7842(5)
8520(8)
9320(8)
8294(8)
49(2)
74(3)
58(2)
55(2)
85(3)
64(2)
89(3)
75(3)
70(3)
103(4)
53(2)
70(2)
97(3)
101(3)
103(3)
54(2)
109(3)
143(4)
150(4)
Pd(2)
O(1)
O(2)
O(3)
O(4)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
2467(10) 8560(6)
8145(6)
9169(9)
9014(10) 5937(8)
9845(10) 5606(8)
9868(13) 6710(8)
9962(15) 4648(7)
10486(15) 4381(11) 5862(12) 192(8)
10322(15) 3707(11) 6069(12) 202(8)
6275(4)
6067(8)
8702(10) 169(5)
5100(12) 167(6)
OOCMe)4Co(OOCR)– in which it would be possible to
follow the effect of electronic and steric features of the
substituent R on the structure of the resulting compounds.
However, unexpectedly, the reactions of 1 with
mononuclear complexes [Pd(Hdmpz)4] (OOCR)2 in
acetonitrile at room temperature resulted in deproto-
nation of palladium-coordinated Hdmpz to give
binuclear
pyrazolate-bridged
complexes
Pd2(µ-dmpz)2(Hdmpz)2(OOCR)2 (R = Me (2), But
(3), and Ph (4)) in high yield:
Me
Me
Me
C
Me
C
O
O
O
O
O
N
N
Me
Pd
Co
NCMe
N
Me
N
O
O
O
O
Pd
Pd
C
Me
C
Me
O
C
R
Pd(Hdmpz)4(OOCR)2
N
H
O
MeCN, T
r.t.
N
R
C
Me
O
Me
N
N
Me
H
Me
R = Me (2), But (3), Ph (4)
According to X-ray diffraction data, the Pd(II) the bridging deprotonated pyrazole molecules (Pd(1)–
atoms in 2 · MeCN are located at a non-bonding dis- N(1), 2.004(2); Pd(1)–N(3), 1.992(2); Pd(2)–N(2),
…
tance (Pd(1) Pd(2) 3.2549(3) Å) and have a square 1.988(2) Å; Pd(2)–N(4), 1.993(2) Å), the pyridine
planar environment composed of two nitrogen atoms of nitrogen atom of the Hdmpz molecule (Pd(1)–N(5),
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 10 2009

FORMATION OF BINUCLEAR PYRAZOLATE-BRIDGED PALLADIUM CARBOXYLATES
1597
Table 7. Bond lengths (d) and bond angles (ω) for complex 3 · C6H14
Bond
d, Å
Bond
d, Å
Angle
ω, deg
N(7)Pd(2)Pd(1) 114.77(17) O(3)Pd(2)Pd(1) 122.15(15)
C(21)O(1)Pd(1) 120.8(5) C(26)O(3)Pd(2) 123.2(5)
Angle
ω, deg
Pd(1)–N(1)
Pd(1)–N(5)
Pd(1)–Pd(2)
Pd(2)–N(2)
Pd(2)–O(3)
O(2)–C(21)
O(4)–C(26)
N(1)–N(2)
1.988(6)
2.009(6)
3.2488(8)
2.001(6)
2.011(5)
1.217(10)
1.234(9)
1.365(7)
1.340(9)
1.349(9)
1.351(8)
1.332(9)
1.349(11)
1.501(10)
1.494(11)
1.477(11)
1.487(11)
1.474(11)
1.495(12)
1.491(12)
1.492(12)
1.506(13)
1.519(13)
1.380(16)
1.517(18)
Pd(1)–N(3)
Pd(1)–O(1)
Pd(2)–N(4)
Pd(2)–N(7)
O(1)–C(21)
O(3)–C(26)
N(1)–C(1)
1.990(6)
2.014(5)
1.987(6)
2.006(6)
1.245(9)
1.256(9)
1.345(9)
1.344(9)
1.347(8)
1.332(8)
1.332(9)
1.342(8)
C(1)N(1)N(2)
N(2)N(1)Pd(1)
C(4)N(2)Pd(2)
C(6)N(3)N(4)
N(4)N(3)Pd(1)
N(3)N(4)Pd(2)
C(11)N(5)N(6)
N(6)N(5)Pd(1)
C(16)N(7)N(8)
N(8)N(7)Pd(2)
107.5(6)
117.9(5)
133.0(5)
108.4(6)
119.1(4)
118.0(4)
106.2(6)
120.6(4)
104.9(7)
120.2(5)
109.0(7)
130.3(8)
108.0(7)
131.1(8)
121.5(7)
106.8(8)
121.0(8)
C(1)N(1)Pd(1)
C(4)N(2)N(1)
N(1)N(2)Pd(2)
C(6)N(3)Pd(1)
N(3)N(4)C(9)
C(9)N(4)Pd(2)
134.5(5)
108.5(6)
118.5(5)
132.5(5)
108.8(6)
133.1(6)
N(2)–C(4)
N(3)–C(6)
N(3)–N(4)
N(5)–C(11)
N(6)–C(14)
N(7)–N(8)
C(1)–C(3)
C(11)N(5)Pd(1) 133.2(5)
C(14)N(6)N(5) 111.5(6)
C(16)N(7)Pd(2) 134.5(6)
N(4)–C(9)
N(5)–N(6)
N(7)–C(16)
N(8)–C(19)
C(1)–C(2)
N(7)N(8)C(19)
N(1)C(1)C(2)
C(1)C(3)C(4)
N(2)C(4)C(5)
N(3)C(6)C(8)
C(8)C(6)C(7)
N(4)C(9)C(8)
C(8)C(9)C(10)
112.3(7)
120.6(7)
106.9(7)
120.9(8)
107.9(7)
130.6(8)
108.1(7)
130.9(8)
1.360(10) N(1)C(1)C(3)
1.375(11) C(3)C(1)C(2)
1.387(10) N(2)C(4)C(3)
1.359(11) C(3)C(4)C(5)
1.373(11) N(3)C(6)C(7)
1.377(11) C(9)C(8)C(6)
1.374(12) N(4)C(9)C(10)
C(3)–C(4)
C(4)–C(5)
C(6)–C(8)
C(6)–C(7)
C(8)–C(9)
C(9)–C(10)
C(11)–C(12)
C(14)–C(15)
C(16)–C(17)
C(19)–C(20)
C(22)–C(25)
C(22)–C(24)
C(27)–C(29)
C(27)–C(30)
C(11)–C(13)
C(13)–C(14)
C(16)–C(18)
C(18)–C(19)
C(21)–C(22)
C(22)–C(23)
C(26)–C(27)
C(27)–C(28)
1.347(12) N(5)C(11)C(13) 109.3(7)
1.549(11) C(13)C(11)C(12) 129.1(7)
1.518(13) N(6)C(14)C(13) 106.0(7)
1.496(13) C(13)C(14)C(15) 132.7(8)
1.446(16) N(7)C(16)C(17) 120.2(9)
C(19)C(18)C(16) 107.8(8)
N(5)C(11)C(12) 121.6(7)
C(11)C(13)C(14) 107.1(7)
N(6)C(14)C(15) 121.2(8)
N(7)C(16)C(18) 109.7(7)
C(18)C(16)C(17) 130.0(8)
C(18)C(19)N(8) 105.2(8)
Angle
ω, deg
Angle
ω, deg
C(18)C(19)C(20) 133.7(9)
O(2)C(21)O(1) 125.8(8)
N(8)C(19)C(20) 121.0(8)
N(1)Pd(1)N(3)
N(3)Pd(1)N(5)
89.2(2)
89.9(2)
N(1)Pd(1)N(5) 177.2(2)
O(2)C(21)C(22) 118.5(8)
C(25)C(22)C(23) 108.2(9)
C(23)C(22)C(24) 108.3(9)
C(23)C(22)C(21) 110.8(8)
O(4)C(26)-O(3) 124.5(8)
O(3)C(26)C(27) 116.9(8)
C(29)C(27)C(26) 115.8(11)
C(29)C(27)C(30) 102.9(12)
C(26)C(27)C(30) 104.2(11)
N(1)Pd(1)O(1)
N(5)Pd(1)O(1)
92.0(2)
89.1(2)
O(1)C(21)C(22) 115.7(8)
C(25)C(22)C(24) 112.0(9)
N(3)Pd(1)O(1) 176.5(2)
N(1)Pd(1)Pd(2)
N(5)Pd(1)Pd(2) 115.12(17) O(1)Pd(1)Pd(2) 122.21(14) C(24)C(22)C(21) 107.2(7)
62.13(17) N(3)Pd(1)Pd(2) 61.17(17) C(25)C(22)C(21) 110.2(8)
N(4)Pd(2)N(2)
N(2)Pd(2)N(7)
88.3(2)
91.9(2)
N(4)Pd(2)N(7) 175.8(2)
O(4)C(26)C(27) 118.7(9)
C(29)C(27)C(28) 114.9(13)
C(28)C(27)C(26) 114.9(10)
N(4)Pd(2)O(3)
N(7)Pd(2)O(3)
92.0(2)
88.2(2)
N(2)Pd(2)O(3) 175.8(2)
N(4)Pd(2)Pd(1)
61.69(17) N(2)Pd(2)Pd(1) 61.50(17) C(28)C(27)C(30) 101.4(13)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 10 2009

1598
PEROVA et al.
Table 8. Atomic coordinates (×104) and equivalent isotropic
factors (Å2, ×103) for complex 4
2.016(2) Å; Pd(2)–N(7), 2.007(2) Å), and the terminal
acetate anion (Pd(1)–O(1), 2.015(2) Å; Pd(2)–O(3),
2.026 Å).
Atom
x
y
z
Ueq
The hydrogen atoms of the NH fragments of the
coordinated Hdmpz molecules form short hydrogen
bonds with the oxygen atoms of acetate anions coordi-
nated to the other palladium(II) atom (N···O 2.688(3),
2.709(3) Å, H–O 1.84, 1.85 Å) similar to the H-bonds
formed in the copper(II) square planar complex
(Hdmpz)2Cu(µ-dmpz)2(OOCBut)2 [6, 17]. It is notewor-
thy that the acetonitrile molecule of solvation present in
the crystal cell does not form intermolecular hydrogen
bonds, unlike that in the nickel complex
Ni2(µ-OOCMe)4(Hdmpz)2 · 2NCMe [6, 18].
The replacement of acetate anions by more basic
pivalate anions in complex 3 (Fig. 2) has almost no
effect on its geometry. Thus, according to X-ray dif-
fraction data, the Pd···Pd distance (3.2546(1) Å) is also
nonbonding; the Pd–N bond lengths of pyrazolate
anions (Pd(1)–N(2), 1.997(5) Å; Pd(1)–N(4),
2.006(5) Å; Pd(2)–N(1), 2.001(5) Å; Pd(2)–N(3),
1.995(6) Å) are close to those found in 3; finally, the
lengths Pd–O and Pd–N bonds with the terminal pyra-
zole molecule and pivalate anion almost do not change
(Pd(1)–O(1), 2.013(4) Å; Pd(1)–N(5), 2.016(5) Å;
Pd(2)–O(3), 2.004(5) Å; Pd(2)–N(7), 2.026(5) Å). The
crystal cell of complex 3 was also found to contain an
acetonitrile molecule of solvation, the intramolecular
hydrogen bonds being similar to those in 2 (O···N,
2.708(6), 2.727(6) Å; H–O, 1.84, 1.85 Å).
Pd(1)
Pd(2)
O(1)
O(2)
O(3)
O(4)
N(1)
N(2)
N(3)
N(4)
N(5)
N(6)
N(7)
N(8)
C(1)
C(2)
C(3)
–205(1)
–148(1)
1457(3)
2914(3)
700(3)
1801(4)
–885(3)
–914(3)
–1939(3)
–1900(3)
477(3)
807(4)
1652(3)
2642(3)
–1361(4) 10330(3)
–1499(5) 11321(3)
–1625(4) 10215(3)
–1311(4)
–1451(4)
–3265(4)
–3668(5)
–4083(4)
–3199(4)
–3521(5)
408(4)
19(5)
735(5)
984(5)
1369(7)
7028(1)
8822(1)
6616(2)
7692(2)
8345(2)
6629(2)
8585(2)
9337(2)
7392(2)
8109(2)
5470(2)
5228(2)
9505(2)
9272(2)
6880(1)
8039(1)
6007(1)
6264(2)
9211(1)
8982(2)
6388(2)
6884(2)
7700(2)
8208(2)
7431(2)
8235(2)
7814(2)
7184(2)
6429(2)
6805(2)
5634(2)
5631(2)
4943(2)
7872(2)
7401(3)
8500(2)
8696(2)
9299(2)
7174(2)
6305(3)
7844(3)
8507(3)
9385(3)
8119(2)
8806(2)
7669(2)
7085(2)
6454(2)
5866(2)
5129(2)
4931(2)
4260(2)
3787(2)
3979(2)
4645(2)
9387(2)
25(1)
25(1)
32(1)
38(1)
33(1)
61(1)
23(1)
24(1)
26(1)
26(1)
34(1)
38(1)
27(1)
28(1)
27(1)
37(1)
28(1)
26(1)
35(1)
32(1)
41(1)
38(1)
31(1)
41(1)
38(1)
50(1)
50(1)
48(1)
67(1)
33(1)
48(1)
36(1)
32(1)
42(1)
28(1)
29(1)
36(1)
43(1)
41(1)
40(1)
32(1)
38(1)
52(1)
76(1)
94(2)
96(2)
83(1)
61(1)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
9102(3)
8513(3)
7060(3)
6279(3)
7565(3)
8227(3)
8995(3)
4556(3)
4546(3)
3729(3)
4170(3)
3708(4)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
Note that 3 is soluble in nonpolar organic solvents.
Its recrystallizastion gave single crystals containing a
hexane molecule of solvation. The replacement of the
solvation molecule does not result in considerable
changes in the complex geometry (Pd···Pd 3.2488(8),
Pd–µ-N, 1.987(6)–2.001(6) Å; Pd–N, 2.006(6)–
2.0013(6) Å; Pd–O, 2.011(5)–2.014(5) Å) or the char-
acter of intramolecular hydrogen bonds (O···N 2.711(6),
2.723(6) Å; H–O, 1.82, 1.83 Å).
2027(4) 10297(3)
1119(6) 10788(3)
3292(4) 10542(3)
Finally, the appearance of more sterically crowded
and the least basic benzoate anion (complex 4, Fig. 3)
only slightly increases the metal–metal distance (to
2.2637(4) Å), while the geometry of the rest of the
complex (Pd–µ-N, 1.988(2)–1.995(3) Å; Pd–N,
2.012(3)–2.016(3) Å; Pd–O, 2.023(2)–2.029(2) Å) and
the intramolecular hydrogen bonds (O···N 2.701(3)–
2.706(3) Å; H–O, 1.83, 1.86 Å) are retained.
3666(4)
4944(4)
2598(4)
3609(4)
4894(4)
5833(5)
5494(5)
4201(5)
3263(4)
1652(5)
2652(5)
3525(6)
4552(7)
4628(7)
3826(6)
2828(5)
9873(3)
9718(3)
7053(3)
6748(3)
7164(3)
6893(3)
6196(3)
5794(3)
6066(3)
7369(3)
7154(4) 10153(2)
6099(5) 10469(3)
5882(6) 11167(4)
6745(6) 11515(4)
7818(6) 11198(3)
8002(5) 10515(3)
Previously, analogous complexes were obtained in
reactions of Pd2(µ-dmpz)2(dmpz)2(Hdmpz)2 with ben-
zoic acid derivatives H2CC6H4–R (R = m-NO2,
p-N(CH3)2, p-NH2, p-OCH3, p-OH); their geometry is
almost the same as that found for complex 4 [19]
(Pd···Pd 3.269, 3.272; Pd–µ-N, 1.989(2)–2.001(2) Å,
1.986(2)–1.998(2) Å; Pd–N, 2.011(2)–2.016(2),
2.014(2)–2.017(2) Å; Pd–O, 2.001(5)–2.015(2),
2.001(2)–2.004(2) Å for the structurally characterized
p-OCH3 and -OH).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 10 2009

FORMATION OF BINUCLEAR PYRAZOLATE-BRIDGED PALLADIUM CARBOXYLATES
1599
Table 9. Bond lengths (d) and bond angles (ω) for complex 4
Bond
d, Å
Bond
d, Å
Bond
d, Å
Bond
d, Å
Pd(1)–N(1)
Pd(1)–N(5)
Pd(2)–N(2)
Pd(2)–N(7)
O(1)–C(21)
O(3)–C(28)
N(1)–C(4)
N(2)–C(1)
N(3)–N(4)
N(5)–N(6)
N(6)–C(14)
N(7)–C(16)
C(1)–C(3)
C(3)–C(4)
1.989(2) Pd(1)–N(3)
2.016(3) Pd(1)–O(1)
1.988(2) Pd(2)–N(4)
2.012(3) Pd(2)–O(3)
1.279(4) O(2)–C(21)
1.286(4) O(4)–C(28)
1.334(4) N(1)–N(2)
1.348(4) N(3)–C(6)
1.359(4) N(4)–C(9)
1.340(4) N(5)–C(11)
1.352(4) N(7)–N(8)
1.344(4) N(8)–C(19)
1.380(5) C(1)–C(2)
1.399(5) C(4)–C(5)
1.989(3) C(6)–C(8)
2.023(2) C(8)–C(9)
1.995(3) C(11)–C(13)
2.029(2) C(13)–C(14)
1.235(4) C(16)–C(18)
1.233(5) C(18)–C(19)
1.370(4) C(21)–C(22)
1.349(4) C(22)–C(27)
1.347(4) C(24)–C(25)
1.346(5) C(26)–C(27)
1.341(4) C(29)–C(30)
1.341(4) C(30)–C(31)
1.494(5) C(32)–C(33)
1.496(5)
1.379(5) C(6)–C(7)
1.498(5)
1.484(5)
1.490(6)
1.491(6)
1.479(5)
1.487(5)
1.385(5)
1.384(5)
1.379(5)
1.495(5)
1.386(7)
1.363(9)
1.386(6)
1.392(5) C(9)–C(10)
1.395(5) C(11)–C(12)
1.365(6) C(14)–C(15)
1.392(5) C(16)–C(17)
1.369(5) C(19)–C(20)
1.512(5) C(22)–C(23)
1.386(5) C(23)–C(24)
1.386(5) C(25)–C(26)
1.376(5) C(28)–C(29)
1.384(6) C(29)–C(34)
1.415(7) C(31)–C(32)
1.390(9) C(33)–C(34)
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
Angle
Angle
N(1)Pd(1)N(3) 88.46(10) N(1)Pd(1)N(5) 177.38(12) N(3)C(6)C(7)
121.2(3) C(8)C(6)C(7)
106.0(3) N(4)C(9)C(8)
121.0(3) C(8)C(9)C(10)
108.2(4) N(5)C(11)C(12)
130.0(3)
108.4(3)
130.6(3)
121.1(3)
N(3)Pd(1)N(5) 89.65(12) N(1)Pd(1)O(1)
N(3)Pd(1)O(1) 176.05(10) N(5)Pd(1)O(1)
N(2)Pd(2)N(4) 88.75(11) N(2)Pd(2)N(7)
92.40(10) C(6)C(8)C(9)
89.61(11) N(4)C(9)C(10)
89.15(11) N(5)C(11)C(13)
N(4)Pd(2)N(7) 176.88(11) N(2)Pd(2)O(3) 177.30(10) C(13)C(11)C(12) 130.6(4) C(14)C(13)C(11) 107.2(3)
N(4)Pd(2)O(3) 93.90(10) N(7)Pd(2)O(3)
C(21)O(1)Pd(1) 122.0(2) C(28)O(3)Pd(2) 116.6(2) C(13)C(14)C(15) 132.8(4) N(7)C(16)C(18)
C(4)N(1)N(2) 108.5(2) C(4)N(1)Pd(1) 133.4(2) N(7)C(16)C(17)
N(2)N(1)Pd(1) 118.02(19) C(1)N(2)N(1) 108.5(2) C(19)C(18)C(16) 106.8(3) N(8)C(19)C(18)
132.5(2) N(1)N(2)Pd(2) 118.77(18) N(8)C(19)C(20) 121.5(3) C(18)C(19)C(20) 132.0(3)
126.2(3) O(2)C(21)C(22) 118.9(3)
114.9(3) C(23)C(22)C(27) 119.5(3)
88.23(10) N(6)C(14)C(13)
106.3(4) N(6)C(14)C(15)
120.9(4)
108.5(3)
121.3(3) C(18)C(16)C(17) 130.1(3)
106.4(3)
C(1)N(2)Pd(2)
C(6)N(3)N(4)
N(4)N(3)Pd(1)
C(9)N(4)Pd(2)
N(6)N(5)C(11)
108.3(3) C(6)N(3)Pd(1)
119.7(2) C(9)N(4)N(3)
133.9(2) N(3)N(4)Pd(2)
107.0(3) N(6)N(5)Pd(1)
132.0(2) O(2)C(21)O(1)
108.6(3) O(1)C(21)C(22)
117.3(2) C(23)C(22)C(21) 119.5(3) C(27)C(22)C(21) 121.1(3)
120.4(2) C(24)C(23)C(22) 120.2(3) C(23)C(24)C(25) 119.9(4)
111.1(3) C(26)C(25)C(24) 119.8(4) C(27)C(26)C(25) 120.5(4)
C(11)N(5)Pd(1) 131.5(3) N(5)N(6)C(14)
N(8)N(7)C(16) 106.6(3) N(8)N(7)Pd(2)
C(16)N(7)Pd(2) 132.9(2) N(7)N(8)C(19)
120.0(2) C(26)C(27)C(22) 120.2(3) O(4)C(28)O(3)
111.5(3) O(4)C(28)C(29) 119.3(4) O(3)C(28)C(29)
125.8(3)
114.9(4)
N(2)C(1)C(3)
C(3)C(1)C(2)
N(1)C(4)C(3)
C(3)C(4)C(5)
108.4(3) N(2)C(1)C(2)
130.7(3) C(1)C(3)C(4)
108.5(3) N(1)C(4)C(5)
129.5(3) N(3)C(6)C(8)
120.9(3) C(30)C(29)C(34) 119.3(4) C(30)C(29)C(28) 119.6(5)
106.1(3) C(34)C(29)C(28) 120.9(4) C(29)C(30)C(31) 120.6(6)
122.0(3) C(32)C(31)C(30) 117.5(6) C(31)C(32)C(33) 123.7(6)
108.8(3) C(34)C(33)C(32) 117.2(6) C(29)C(34)C(33) 121.6(5)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 10 2009

1600
PEROVA et al.
C(8)
C(7)
C(6)
C(10)
C(9)
N(4)
N(3)
C(21)
C(22)
O(1)
C(20)
C(19)
C(18)
C(16)
H(8A)
N(2)
N(8)
O(2)
N(7)
Pd(2)
Pd(1)
N(1)
C(17)
C(12)
C(2)
N(5)
C(5)
O(3)
C(23)
C(1)
C(4)
C(3)
C(11)
C(13)
N(6) H(6A)
O(4)
C(14)
C(24)
C(15)
Fig. 1. Structure of complex 2.
C(15)
C(28)
C(14)
C(27)
C(13)
C(30)
O(4)
C(29)
N(6)
C(6)
C(26)
H(6A)
C(11)
N(5)
C(7)
C(8)
C(10)
O(3)
C(9)
C(12)
N(3)
N(4)
Pd(1)
Pd(2)
N(7)
O(1)
C(17)
C(25)
C(16)
O(2)
H(8A)
N(8)
C(21)
N(1)
C(19)
C(22)
C(18)
N(2)
C(23)
C(20)
C(4)
C(24)
C(1)
C(2)
C(5)
C(3)
Fig. 2. Structure of complex 3.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 10 2009

FORMATION OF BINUCLEAR PYRAZOLATE-BRIDGED PALLADIUM CARBOXYLATES
1601
C(3)
C(5)
C(2)
C(4)
N(1)
C(1)
C(25)
C(27)
C(24)
C(20)
C(23)
C(21)
N(2)
N(8)
C(26)
C(19)
C(18)
C(16)
O(2)
C(22)
O(1)
N(7)
Pd(2)
C(17)
Pd(1)
N(3)
N(4)
C(10)
O(3)
C(7)
N(5)
C(12)
C(6)
C(9)
C(8)
C(11)
C(34)
O(4)
N(6)
C(14)
C(29)
C(13)
C(33)
C(30)
C(15)
C(32)
C(31)
Fig. 3. Structure of complex 4.
Thus, we found that instead of the expected replace- “Targeted Synthesis of Inorganic Compounds and
ment of labile acetonitrile by two-electron carboxylate Design of Functional Materials”).
anion, the considered reaction occurs as deprotonation
of the palladium-coordinated pyrazole with destruction
of the heterometallic complex 1 and generation of ace-
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temperature where, instead of coordination of the N2Ph2
molecule to the metal, its ortho-metallation takes place
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(2006).
7. N. Yu. Kozitsyna, S. E. Nefedov, F. M. Dolgushin, et al.,
This work was supported by the Russian Foundation
for Basic Research (project nos. 08-03-01063 and 08-
03-90455), the Council of the President of the Russian
Federation for Support of Leading Scientific Schools of
Russia, grant NSh-1733.2008.3), Presidium and the
Division of Chemistry and Material Science of the RAS
(the programs “Theoretical and Experimental Study of
the Nature of Chemical Bond and Mechanisms of
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