**5. Modification of polyurethanes by heteronuclear complexes based on molybdenum (V) and copper (II) chlorides**

To study the effect of the coordination compounds structure on the electrophysical properties of the modified polyurethanes the heteronuclear metal complexes based on transition metals of IV and V periods were synthesized. CuCl2 was used as the chloride of 3d-metal, and MoCl5 was used as the chloride of the 4d-metal. DEHA was used as a ligand. Cu (II) has 3d-orbitals that are involved in coordinating binding, in the case of Mo (V) this role is performed by 4d-orbitals. Therefore, it is assumed that when heteronuclear complexes of the columnar structure are formed, where the CuCl2 is in excess, the ions of molybdenum could cause the interruption of chains of exchange interactions between 3dions (Fig. 7). It is found that the metal complex system, obtained on the basis of [CuCl2]:[DEHA] = 1:0,7 has *ρv* = 2600 Ohm. sm at room temperature, while the system based on [MoCl5]:[DEHA] = 1:0,7 has *ρv* = 1300 Ohm. sm. The heteronuclear complex obtained at the ratio of [CuCl2]:[MoCl5]:[DEHA] = 0,9:0,1:0,7 at room temperature exhibits *ρv* = 5250 Ohm. sm, while the complex obtained at ratio of [CuCl2]:[MoCl5]:[DEHA] = 0,8:0,2:0,7 has already *ρv* = 73800 Ohm. sm.

Homonuclear and heteronuclear metal complexes were used for polyurethane modification. It was found that both modifying systems were able to react with the urethane prepolymer. When the metal complex structuring of polyurethanes by heteronuclear complexes based on 3d-and 4d-ions took place ρv values remained similar to the unmodified sample. With the increase of the concentration of heteronuclear complex the specific volume electrical resistance of polyurethanes actually increased slightly (Fig. 8). Another situation is observed in the case of polyurethanes modification by homonuclear coordination compounds. In this case the introduction of metal complexes based on copper led to the decrease of ρv by three orders. However, when polyurethanes were modified by homonuclear metal complex compounds based on Mo (V) ρv decreased by 5 orders.

Ar N N Ar

Cl Cu Cl

Ar N N Ar

Cl Cu Cl

Ohm.

already *ρv* = 73800 Ohm.

Ar N N Ar

**Figure 6.** Formation of columnar coordination compounds.

**molybdenum (V) and copper (II) chlorides** 

[CuCl2]:[DEHA] = 1:0,7 has *ρv* = 2600 Ohm.

on [MoCl5]:[DEHA] = 1:0,7 has *ρv* = 1300 Ohm.

sm.

compounds based on Mo (V) ρv decreased by 5 orders.

, where Ar -

**5. Modification of polyurethanes by heteronuclear complexes based on** 

To study the effect of the coordination compounds structure on the electrophysical properties of the modified polyurethanes the heteronuclear metal complexes based on transition metals of IV and V periods were synthesized. CuCl2 was used as the chloride of 3d-metal, and MoCl5 was used as the chloride of the 4d-metal. DEHA was used as a ligand. Cu (II) has 3d-orbitals that are involved in coordinating binding, in the case of Mo (V) this role is performed by 4d-orbitals. Therefore, it is assumed that when heteronuclear complexes of the columnar structure are formed, where the CuCl2 is in excess, the ions of molybdenum could cause the interruption of chains of exchange interactions between 3dions (Fig. 7). It is found that the metal complex system, obtained on the basis of

the ratio of [CuCl2]:[MoCl5]:[DEHA] = 0,9:0,1:0,7 at room temperature exhibits *ρv* = 5250

Homonuclear and heteronuclear metal complexes were used for polyurethane modification. It was found that both modifying systems were able to react with the urethane prepolymer. When the metal complex structuring of polyurethanes by heteronuclear complexes based on 3d-and 4d-ions took place ρv values remained similar to the unmodified sample. With the increase of the concentration of heteronuclear complex the specific volume electrical resistance of polyurethanes actually increased slightly (Fig. 8). Another situation is observed in the case of polyurethanes modification by homonuclear coordination compounds. In this case the introduction of metal complexes based on copper led to the decrease of ρv by three orders. However, when polyurethanes were modified by homonuclear metal complex

sm, while the complex obtained at ratio of [CuCl2]:[MoCl5]:[DEHA] = 0,8:0,2:0,7 has

NCO

O C HN O

CH3

sm at room temperature, while the system based

sm. The heteronuclear complex obtained at

, ,

NCO

CH3

NCO ,

Cl Cu Cl

Cl Cu Cl

Ar N N Ar

Ar N N Ar

**Figure 7.** Scheme of the formation of columnar homonuclear and heteronuclear coordination compounds of transition metal.

**Figure 8.** Dependence of *ρv* (Ohm. sm) of polyurethanes on the concentration (%) of metal complexes based on: 1-MoCl5-DEHA; 2-CuCl2-DEHA; 3-CuCl2-MoCl5-DEHA.
