The paper describes some chemical transformations of the mixed-metal palladium (II) complexes, including
interactions of binuclear complexes with pyridine, 1,10-phenanthroline and bipyridine; also described
thermal and reductive transformations of some binuclear and pentanuclear nitrogen-containing
complexes, in particular red-ox transformations in reductive media to yield mixed-metal nanomaterials.
For this nanomaterials and nanoalloys also provided HREM and TEM investigations.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3523

Kondratyeva, O.N.

Kozitsyna, N.Y.

Moiseev, I.I.

Vargaftik, M.N.

Yakushev, I.A.

Electronic Sumy State University Institutional Repository

MIXED-METAL PALLADIUM(II) COMPLEXES : A WAY FROM HETEROBIMETALLIC COMPLEXES TO NANOPARTICLES Vol. 2 No 2, 02PCN35(3pp) (2013)   2304-1862/2013/2(2)02PCN35(3) 02PCN35-1  2013 Sumy State University Mixed-Metal Palladium(II) Complexes: a Way from Heterometallic  Carboxylates to Bimetallic Nanoparticles  I.A. Yakushev*, N.Yu. Kozitsyna, O.N. Kondratyeva, S.E. Nefedov, V.K. Ivanov,  M.N. Vargaftik, I.I. Moiseev  Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, 31, Leninsky prospect, 119991 Moscow, Russia  (Received 14 June 2013; published online 03 September 2013)  The paper describes some chemical transformations of the mixed-metal palladium (II) complexes, in-cluding interactions of binuclear complexes with pyridine, 1,10-phenanthroline and bipyridine; also de-scribed thermal and reductive transformations of some binuclear and pentanuclear nitrogen-containing complexes, in particular red-ox transformations in reductive media to yield mixed-metal nanomaterials. For this nanomaterials and nanoalloys also provided HREM and TEM investigations.  Keywords: Palladium, Transition Metals, Thermal Conversions, Reduction under Mild Conditions.     PACS numbers: 68.37.Hk, 81.07.Bc, 81.10.Dn   1. INTRODUCTION  Palladium-based heterometallic carboxylates seem to be handy precursors of nanoalloys and mixed-metal catalysts [1]. Earlier we used for this purpose PdII-based heterobimetallic complexes containing the alkaline-earth (Ca, Sr, Ba) [2], transition (MnII,CoII, NiII, CuII) [2, 3], post-transition (ZnII) [3] and rare-earth (CeIV, NdIII, EuIII, SmIII) metals [4, 5] .(Fig. 1) in which the Pd to complementary metal (M) ratio is 1:1. In this work we prepared and studied new PdII-based heterometallic carboxylates with a Pd:M ratio of 3:2.  Pd3(OOCMe)6M(OOCMe)n+M = CuM = Nd, EuM = Co, NiL = NCMeM = Mn, ZnL = OH2n = 3n = 2n = 2 Fig. 1  2. REACTIONS WITH N-DONOR LIGANDS  With this purpose we studied a reactivity and coordi-nation abilities of 1:1 PdII- based binuclear complexes towards N-bases, pyridine (Py), 1,10-phenanthroline (Phen) and 2,2’-bipyridine (bipy).  Reaction of 1,10-phenanthroline or 2,2’-bipyridine with the binuclear complexes gives isostructural binu-clear complexes Pd(μ-OOCMe)3(η-*OOC-                                               * cs68@mail.ru Me)M(Phen)?2MeCN (M  Zn, Ni, Co) with three bridg-ing acetate ligands and a short Pd–M distance (Pd∙∙∙Zn 2.7004(9); Pd∙∙∙Ni 2.6021(7); Pd∙∙∙Co 2.6952(9) ). Similar complex was obtained by the reaction of PdCo(OOCMe)4MeCN with 2,2’-bipyridine (Pd∙∙∙Co dis-tance is 2.6748(9)) (Fig. 2).  The reaction of PdMn(µ-OOCMe)4(OH2) with Phen produced Pd(µ-OOCMe)4Mn(Phen) with four bridging acetate groups and a Pd–Mn distance of 2.8425(5). The reaction of PdZn(OOCMe)4(OH2) with I.A. YAKUSHEV, N.YU. KOZITSYNA, ET AL. PROC. NAP 2, 02PCN35 (2013)   02PCN35-2 Bipy gave (Bipy)Pd(µ-OOCMe)2Zn(η-OOCMe)2, in which two acetate bridges support the binuclear struc-ture (Fig. 3).    Fig. 2    Fig. 3  Unlike these, monodentate N-donor pyridine with-draws PdII atom from some of the binuclear complexes and the Pd(Py)2(OOCMe)2 species formed links the re-sidual intact binuclear complexes, producing the pen-tanuclear complex [PdM(OOCMe)4]2Pd(Py)2(OOCMe)2 (Pd3M2, M = Co, Ni, Mn, Zn) with the Pd(Py)2(OOCMe)2 linker (Fig. 4) [6].   Fig. 4   3. REDUCTIVE THERMOLYSIS OF PENTANUCLEAR COMPLEXES   The obtained pentanuclear complexes [PdM(OAc)4]2Pd(Py)2(OOCMe)2 (M=Co, Ni, Mn, Zn) were thermally decomposed in a 10% H2–He stream, by heating from room temperature to 600?C with the heat-ing rate 20?C/min. XRD of the solid products showed that in all cases at least one non-segregated phase cor-responding to a nanoalloy.  3.1 Electron micrographs of the solid products of reduction  The nanomaterials obtained by reduction of the pen-tanuclear complexes were studied by SEM and HREM, (see Fig. 5, HREM for Pd3Co2) and (Fig. 6, SEM for Pd3Co2, Fig. 7 SEM for Pd3Mn2).    Fig. 5    Fig. 6   Fig. 7  3.2 Unexpected formation of bipyridine  Study of the gas-phase products of the thermal de-composition of the pentanuclear Pd3M2(Py)2(OAc)10 and mononuclear Pd(Py)2(OAc)2 complexes (Finnigan MAT  MIXED-METAL PALLADIUM(II) COMPLEXES… PROC. NAP 2, 02PCN35 (2013)   02PCN35-3 INCOS 50 mass-spectrometer, direct probe input, heat-ing 50–250 C) unexpectedly revealed the formation of bipyridine, the mononuclear Pd(Py)2(OAc)2 (Table 1).  Table 1   Complex Yield, % [PdCo(OOCMe)4]2Pd(C5H5N)2(OOCMe)2 0.32 [PdNi(OOCMe)4]2Pd(C5H5N)2(OOCMe)2 1.47 [PdZn(OOCMe)4]2Pd(C5H5N)2(OOCMe)2 3.26 [PdMn(OOCMe)4]2Pd(C5H5N)2(OOCMe)2 11.5 Pd(C5H5N)2(OOCMe)2  1.68 AKNOWLEDGEMENTS  Authors are grateful for financial support to the RFBR (Projects №№ 13-03-00408, 12-03-31325, 12-03-00917), the Foundation of President of the Russian Federation (program for support of leading Russian scientific schools NSh-5232.2012.3) and the Foundation of the Russian Academy of Sciences ("Development of methods for the preparation of chemicals and new ma-terials" and "The fundamentals of technology of nanostructures and nanomaterials").   REFERENCES  1. N.Yu. Kozitsyna, S.E. Nefedov, Zh.V. Dobrokhotova, V.N. Ikorsky, I.P Stolyarov, M.N. Vargaftik, I.I. Moiseev, Nanotechnologies in Russia 3, Nos 3-4, 166 (2008). 2. N.Yu. Kozityna, S.E. Nefedov, I.A. Yakushev, Z.V. Dobrokhotova, M.N. Vargaftik, I.I. Moiseev, Mendele-ev Comm. 17, No 5, 261-263 (2007). 3. N.Yu. Kozitsyna, S.E. Nefedov, N.V. Cherkashina, V.N. Ikorski, M.N. Vargaftik, I.I. Moiseev, Russ. Chem. Bull. 54, 2215 (2005). 4. N.Yu. Kozitsyna, S.E. Nefedov, F.M. Dolgushin, N.V. Cherkashina, M.N. Vargaftik, I.I. Moiseev, Inorg. Chim. Acta 359, 2072 (2006). 5. N.Yu. Kozitsyna, S.E. Nefedov, M.N. Vargaftik, I.I. Moiseev, Mendeleev Commun. 15, 223 (2005). 6. S.E. Nefedov, I.A. Yakushev, N.Yu. Kozityna, Zh.V. Dobrokhotova, V.N. Ikorsky, M.N. Vargaftik, I.I. Moiseev. Inorg. Chem. Comm. 10, 948–951 (2007).  

Mixed-Metal Palladium(II) Complexes: a Way from Heterometallic Carboxylates to Bimetallic Nanoparticles

SocioEconomic Challenges Journal (Sumy State University)

MIXED-METAL PALLADIUM(II) COMPLEXES : 
A WAY FROM HETEROBIMETALLIC COMPLEXES TO NANOPARTICLES 
Vol. 2 No 2, 02PCN35(3pp) (2013) 
 
 
2304-1862/2013/2(2)02PCN35(3) 02PCN35-1  2013 Sumy State University 
Mixed-Metal Palladium(II) Complexes: a Way from Heterometallic  
Carboxylates to Bimetallic Nanoparticles 
 
I.A. Yakushev*, N.Yu. Kozitsyna, O.N. Kondratyeva, S.E. Nefedov, V.K. Ivanov,  
M.N. Vargaftik, I.I. Moiseev 
 
Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, 31, Leninsky prospect, 
119991 Moscow, Russia 
 
(Received 14 June 2013; published online 03 September 2013) 
 
The paper describes some chemical transformations of the mixed-metal palladium (II) complexes, in-
cluding interactions of binuclear complexes with pyridine, 1,10-phenanthroline and bipyridine; also de-
scribed thermal and reductive transformations of some binuclear and pentanuclear nitrogen-containing 
complexes, in particular red-ox transformations in reductive media to yield mixed-metal nanomaterials. 
For this nanomaterials and nanoalloys also provided HREM and TEM investigations. 
 
Keywords: Palladium, Transition Metals, Thermal Conversions, Reduction under Mild Conditions.  
 
  PACS numbers: 68.37.Hk, 81.07.Bc, 81.10.Dn 
 
 
1. INTRODUCTION 
 
Palladium-based heterometallic carboxylates seem 
to be handy precursors of nanoalloys and mixed-metal 
catalysts [1]. Earlier we used for this purpose PdII-
based heterobimetallic complexes containing the 
alkaline-earth (Ca, Sr, Ba) [2], transition (MnII,CoII, 
NiII, CuII) [2, 3], post-transition (ZnII) [3] and rare-earth 
(CeIV, NdIII, EuIII, SmIII) metals [4, 5] .(Fig. 1) in which 
the Pd to complementary metal (M) ratio is 1:1. In this 
work we prepared and studied new PdII-based 
heterometallic carboxylates with a Pd:M ratio of 3:2. 
 
Pd3(OOCMe)6
M(OOCMe)n
+
M = Cu
M = Nd, Eu
M = Co, Ni
L = NCMe
M = Mn, Zn
L = OH2
n = 3
n = 2
n = 2
 
Fig. 1 
 
2. REACTIONS WITH N-DONOR LIGANDS 
 
With this purpose we studied a reactivity and coordi-
nation abilities of 1:1 PdII- based binuclear complexes 
towards N-bases, pyridine (Py), 1,10-phenanthroline 
(Phen) and 2,2’-bipyridine (bipy).  
Reaction of 1,10-phenanthroline or 2,2’-bipyridine 
with the binuclear complexes gives isostructural binu-
clear complexes Pd(μ-OOCMe)3(η-*OOC-
                                               
*
 cs68@mail.ru 
Me)M(Phen)?2MeCN (M  Zn, Ni, Co) with three bridg-
ing acetate ligands and a short Pd–M distance (Pd∙∙∙Zn 
2.7004(9); Pd∙∙∙Ni 2.6021(7); Pd∙∙∙Co 2.6952(9) ). Similar 
complex was obtained by the reaction of 
PdCo(OOCMe)4MeCN with 2,2’-bipyridine (Pd∙∙∙Co dis-
tance is 2.6748(9)) (Fig. 2).  
The reaction of PdMn(µ-OOCMe)4(OH2) with Phen 
produced Pd(µ-OOCMe)4Mn(Phen) with four bridging 
acetate groups and a Pd–Mn distance of 2.8425(5). The 
reaction of PdZn(OOCMe)4(OH2) with
 I.A. YAKUSHEV, N.YU. KOZITSYNA, ET AL. PROC. NAP 2, 02PCN35 (2013) 
 
 
02PCN35-2 
Bipy gave (Bipy)Pd(µ-OOCMe)2Zn(η-OOCMe)2, in 
which two acetate bridges support the binuclear struc-
ture (Fig. 3). 
 
 
 
Fig. 2 
 
 
 
Fig. 3 
 
Unlike these, monodentate N-donor pyridine with-
draws PdII atom from some of the binuclear complexes 
and the Pd(Py)2(OOCMe)2 species formed links the re-
sidual intact binuclear complexes, producing the pen-
tanuclear complex [PdM(OOCMe)4]2Pd(Py)2(OOCMe)2 
(Pd3M2, M = Co, Ni, Mn, Zn) with the Pd(Py)2(OOCMe)2 
linker (Fig. 4) [6]. 
 
 
Fig. 4 
 
 
3. REDUCTIVE THERMOLYSIS OF 
PENTANUCLEAR COMPLEXES  
 
The obtained pentanuclear complexes 
[PdM(OAc)4]2Pd(Py)2(OOCMe)2 (M=Co, Ni, Mn, Zn) 
were thermally decomposed in a 10% H2–He stream, by 
heating from room temperature to 600?C with the heat-
ing rate 20?C/min. XRD of the solid products showed 
that in all cases at least one non-segregated phase cor-
responding to a nanoalloy. 
 
3.1 Electron micrographs of the solid products 
of reduction 
 
The nanomaterials obtained by reduction of the pen-
tanuclear complexes were studied by SEM and HREM, 
(see Fig. 5, HREM for Pd3Co2) and (Fig. 6, SEM for 
Pd3Co2, Fig. 7 SEM for Pd3Mn2). 
 
 
 
Fig. 5 
 
 
 
Fig. 6 
 
 
Fig. 7 
 
3.2 Unexpected formation of bipyridine 
 
Study of the gas-phase products of the thermal de-
composition of the pentanuclear Pd3M2(Py)2(OAc)10 and 
mononuclear Pd(Py)2(OAc)2 complexes (Finnigan MAT 
 MIXED-METAL PALLADIUM(II) COMPLEXES… PROC. NAP 2, 02PCN35 (2013) 
 
 
02PCN35-3 
INCOS 50 mass-spectrometer, direct probe input, heat-
ing 50–250 C) unexpectedly revealed the formation of 
bipyridine, the mononuclear Pd(Py)2(OAc)2 (Table 1). 
 
Table 1  
 
Complex Yield, % 
[PdCo(OOCMe)4]2Pd(C5H5N)2(OOCMe)2 0.32 
[PdNi(OOCMe)4]2Pd(C5H5N)2(OOCMe)2 1.47 
[PdZn(OOCMe)4]2Pd(C5H5N)2(OOCMe)2 3.26 
[PdMn(OOCMe)4]2Pd(C5H5N)2(OOCMe)2 11.5 
Pd(C5H5N)2(OOCMe)2  1.68 
AKNOWLEDGEMENTS 
 
Authors are grateful for financial support to the 
RFBR (Projects №№ 13-03-00408, 12-03-31325, 12-03-
00917), the Foundation of President of the Russian 
Federation (program for support of leading Russian 
scientific schools NSh-5232.2012.3) and the Foundation 
of the Russian Academy of Sciences ("Development of 
methods for the preparation of chemicals and new ma-
terials" and "The fundamentals of technology of 
nanostructures and nanomaterials"). 
 
 
REFERENCES 
 
1. N.Yu. Kozitsyna, S.E. Nefedov, Zh.V. Dobrokhotova, 
V.N. Ikorsky, I.P Stolyarov, M.N. Vargaftik, I.I. Moiseev, 
Nanotechnologies in Russia 3, Nos 3-4, 166 (2008). 
2. N.Yu. Kozityna, S.E. Nefedov, I.A. Yakushev, 
Z.V. Dobrokhotova, M.N. Vargaftik, I.I. Moiseev, Mendele-
ev Comm. 17, No 5, 261-263 (2007). 
3. N.Yu. Kozitsyna, S.E. Nefedov, N.V. Cherkashina, 
V.N. Ikorski, M.N. Vargaftik, I.I. Moiseev, Russ. Chem. 
Bull. 54, 2215 (2005). 
4. N.Yu. Kozitsyna, S.E. Nefedov, F.M. Dolgushin, 
N.V. Cherkashina, M.N. Vargaftik, I.I. Moiseev, Inorg. 
Chim. Acta 359, 2072 (2006). 
5. N.Yu. Kozitsyna, S.E. Nefedov, M.N. Vargaftik, 
I.I. Moiseev, Mendeleev Commun. 15, 223 (2005). 
6. S.E. Nefedov, I.A. Yakushev, N.Yu. Kozityna, 
Zh.V. Dobrokhotova, V.N. Ikorsky, M.N. Vargaftik, 
I.I. Moiseev. Inorg. Chem. Comm. 10, 948–951 (2007). 
 


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Mixed-Metal Palladium(II) Complexes: a Way from Heterometallic Carboxylates to Bimetallic Nanoparticles

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