The Insertion of Carbon Dioxide in Combination with RNCS (R Is Et, Ph) or N,N′-Dihexylcarbodiimide into the Re–O(R) Bonds


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Аннотация

The heteromolecular insertion of carbon dioxide in combination with heterocumulenes, iso(thio)cyanates or N,N′-dicyclohexylcarbodiimide, into rhenium–alkoxy group bond was accomplished for the first time in relation to reactivity of rhenium oxoalkoxides. The ease of combined insertion of iso(thio)cyanate and carbon dioxide into Re–O(Me) bond is determined by the nature of the heterocumulene organic group. Indeed, if ethyl iso(thio)cyanate is used in the reaction, the insertion is reversible, whereas the reaction with PhNCS (unlike PhNCO) together with carbon dioxide leads to complete insertion into two Re–O(R) bonds to give the insertion product (OMe)10O6Re4[OC(O){N(Ph)C(S)}2-OMe]2. In similar reactions carried out with N,N′-dicyclohexylcarbodiimide, a dependence of the number of bonds participating in the inner-sphere condensation of the inserted moieties on the duration of the experiment was found for the first time. An increase in the time of synthesis from 3 to 5 h results in insertion involving six rather than three bonds, the heteromolecular insertion products being (OMe),O6Re4{OC(O)[(Hex)N=C=N(Hex)]2}3 and (OMe)6O6Re4{OC(O)[(Hex)N=C=N(Hex)]2}6, respectively.

Об авторах

N. Ovchinnikova

Kurnakov Institute of General and Inorganic Chemistry

Автор, ответственный за переписку.
Email: talan44@mail.ru
Россия, Moscow, 119991

D. Drobot

Moscow Technological University

Email: talan44@mail.ru
Россия, Moscow, 119571

I. Eremenko

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

V. Mulyukina

AO NPP Research and Production Corporation “Toriy”

Email: talan44@mail.ru
Россия, Moscow, 117342

A. Parshakov

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

N. Minaeva

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

G. Aleksandrov

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

G. Kirakosyan

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

I. Yakushev

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

Yu. Mikhailov

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

M. Surazhskaya

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

O. Ellert

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

V. Minin

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

N. Efimov

Kurnakov Institute of General and Inorganic Chemistry

Email: talan44@mail.ru
Россия, Moscow, 119991

E. Kulikova

Moscow Technological University

Email: talan44@mail.ru
Россия, Moscow, 119571

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