Документ взят из кэша поисковой машины. Адрес оригинального документа : http://www.chem.msu.ru/rus/chair/org_w/kmos/zaitseva.pdf Дата изменения: Tue Jun 23 13:22:55 2015 Дата индексирования: Sun Apr 10 14:05:23 2016 Кодировка: Поисковые слова: m 5

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: - - - (, , ) - (, )


: - , ( ) - ( , ) - (, )


M(CO)6
THF hv 3h [R2Ge]M(CO)5 6 R2Ge (1) M(CO)
5 .

(L2H2)
RR NHC6F RN NHC6F R=Me R=Bn
5 1 5

(II), (II)
MR
n

OH N OH RR
1

OH RN OH R1 R
1

+ L2H

2

L2MRn

THF

R'2Ge (4, 5)

[R'2Ge]M(CO)

5

RN

O AlMe O

RR

R"2Ge (2, 3) [R"2Ge]M(CO)5 8, 10, 12 X

14, 16, 18, 20

R=R1=Ph R=Me, R1=Ph

R=Me, R1=H R=Me, R1=Ph OH

N

RR

1

1

C6F5 N RN M R1 AlMe N O C6F5 O
1

Bn R2Ge =

N R"2Ge = 2: 8: 10: 12:

Me

N

N N OH HO

N N H Ts

R=Me, R1=H R=Me, R1=Ph R=Bn, R1=H

R1 R

R=R1=Ph R=Me, R1=Ph Ph Ph

M M M M M

= = = = =

Al, R=Me, R1=Me Al, R=Bn, R1=Me Ge, R=Me, R1Ge, R=Bn, R1Sn, R=Me, R15

Ge N N C6F5 C6F5 6: M=W

NMR Ph Ph M=Al, R=Me M=Ge, Sn, R -

NC6F RN

R'2Ge= Ge O O X=Y=H, 3: X=Me, Y=Ph M=Mo, X=Y=H M=W, X=Y=H M=W, X=Me, Y=Ph

Y Ph Ph

X X

N O Ge O

Ph Ph

4: X=Ph, 5: X=Me 14: M=W, X=Ph 16: M=Mo, X=Ph 18: M=W, X=Me 20: M=Mo, X=Me

AlMe NC6F5 R= M e R=Bn
[R"2Ge]M(CO) 8, 10, 12 Me R " 2Ge = N THF; hv; 5h
5

, ,


R"2Ge (2, 3) X

cis-[R"2Ge]2M(CO) 9, 11, 13

4

2: X=Y=H, 3: X=Me, Y=Ph Y Ph 8, 9: M=Mo, X=Y=H Ph 10, 11: M=W, X=Y=H 12, 13: M=W, X=Me, Y=Ph Ge O O

R3GeNMe2 + (C6F5)3GeH

hexane, heat -HNMe2 R3Ge-Ge(C6F5)3

R = Ph (88%), p-Tol (66%)
(p-Tol)3GeNMe2 + (C6F5)2GeH hexane, heat (p-Tol)3Ge
2

is-[MeN(CH2CPh2O)(CH( Me)CH(Ph)O)Ge]W(CO) 13 . THF;(hv; )5h
[R2Ge]M(CO) 6
5

4

R2Ge 6, 7: M=W Bn N

trans-[R2Ge]2M(CO) 7

4

-HNMe2


(p-Tol)3Ge 51%
Compound

Ge(C6F5)

2

BnN(CH2CH2NC6F5)2AlMe

max (nm)


: - (ROP) - (, )

R2Ge =

( 1) Ge N N C6F C6F5
5

7

(C6F5)3GeGePh

3

226

8

(C6F5)3GeGe(pTo l)3

234

trans-[BnN(CH2CH2NC6F5)2Ge]Mo(CO) (7).
PdL2X2 L L L L =X=PP =PPh3, =CH3C =OAc, [MeN(CH2CH2NC6F5)2Sn]4Pd

4

9

(C6F5)2Ge[Ge(pTo l)3]2

224, 253

(Al, Ti, Zn) (ring-opening polymerization)
L Al O L Al OR L O


MeN(CH2CH2NC6F5)2Sn

h3 X=Cl N, X=Cl X-

(C6F5)3Ge-GePh3

L

Scheme 1
L O (ii) O O RO O Al L

RO (i)

(iii) L RO O macromonomer O H n H2O RO O O Al L

n

(i) Monomer coordination to acidic (on Lewis) metal centre; (ii) Nucleophilic addition of alkoxide group on the carbonyl carbon atom; (iii) Ring opening and repeating steps (i) and (ii).

[MeN(CH2CH2NC6F5)2Sn]4 Pd
R '''O H

2013-2014

R '' N

n N

R ''

R '' N

n N

R ''

Al Al - New oligogermane with a five coordinate germanium atom: The preparation of 1-germylgermatrane. R '''O H = H O ( C H 2) 4O C H = C H 2 R' O O R' R' O O R' Zaitsev, K.V., Churakov, A.V., Poleshchuk, O.K.,Oprunenko, Y.F., Zaitseva, G.S., Karlov, S.S., Dalton 1, 7 : R , R ', R '' = H ; n = 1 O Me 2, 8 : R = H , R ' , R '' = M e; n = 1 Trans., 2014, 43 (18), pp. 6605-6609. R R ''' R R R 3 , 9 : R , R ' = t - B u, R ' ' = H ; n = 1 -Controlled ring-opening homo- and copolymerization of -caprolactone and D,L-lactide by 4 , 1 0 : R , R ' = t - B u, R ' ' = H ; n = 2 7 - 12 1-6 5 , 1 1 : R , R ' = M e , R '' = H ; n =2 iminophenolate aluminum complexes: An efficient approach toward well-defined macromonomers. 6, 1 2 : R , R ', R '' = M e ; n = 2 Zaitsev, K.V., Piskun, Y.A., Oprunenko, Y.F., Karlov, S.S.,Zaitseva, G.S., Vasilenko, I.V., Churakov, A.V., Kostjuk, S.V., J. Polym. Sci., Part A: Polym. Chem., 2014, 52 (9), pp. 1237-1250. - "Donor-acceptor" oligogermanes: Synthesis, structure, and electronic properties. Zaitsev, K.V., : Kapranov, A.A., Churakov, A.V., Poleshchuk, O.K., Oprunenko, Y.F., Tarasevich, B.N., Zaitseva, G.S., 1) 12-03-00206- ( Karlov, S.S., Organometallics, 2013, 32 (21), pp. 6500-6510. ) - Carbonyl complexes of transition metals with stabilized germylenes. Huang, M., Kireenko, M.M., 2) 12-03-90020-_ ( Djevakov, P.B., Zaitsev, K.V., Oprunenko, Y.F., Churakov, A.V., Tyurin, D.A., Karlov, S.S., Zaitseva, G.S., J. Organomet. Chem., 2013, 735, pp. 15-25. Al, Zn Ti ) - Palladium complexes with stabilized germylene and stannylene ligands".Kireenko, M.M., Zaitsev, K.V., 3) 12-03-31153 _ ( 14 (Si, Ge) -: Oprunenko, Y.F., Churakov, A.V., Tafeenko, V.A., Karlov, S.S., Zaitseva, G.S., Dalton Trans., 2013, 42 , - .) (22), pp. 7901-7912.

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