Water soluble alkyl-cobalt chelates as organometallic complex cations

Tetrahedron Lettera No.41, PP. 4005-4007, 1967.

WATER

SOLUBLE

ALKYL-COBALT

CHELATES

G.Costa Department

Perglkmen Resa

of

AS

Ltd.

Printed in Great Britain.

ORGANOHETALLIC

and

G.Mestroni

Chemistry, Trieste,

University Italy

COMPLEX

CATIONS

of Trieste

(Received in UK 13 July 1967)

Dimethylglyoxime' (B)

diimine' cobalt(II1)

and

I

which

can

i,

CHS

I *

more

give

stable

CHI

\,/O

and rings

equatorial organic

the

known the

structures

Co

in the

plane

of

group

R and

The

unusual

attributed to

to

mixing

conjugate

the of

chelate

chelates,with Co(I)

as well

axial

ligand

of Vit.Ban

3 (C) were

<:

used

Q+?=-Q =I I CHz-CHn

'CHs

of nickel,

complexes

an octahedral a Lewis

copper,

stability

proper ligand rings.

cobalt,

v

of

the

-orbitals The

as the

chemical

assumed

to

the

platinum the

be

axial

dimethyl-

arrangement

approximately ligands

of

in the

being

the

L.

adjustment,

in the

pointed

is

structure,

base

cobalt

bond

C

bis(salicylaldehyde)ethylendiimine5 above

to obtain

derivatives.

B

From

chelate

bis(acetylacetone)ethylen-

organo-cobalt

dHp_JHI

A

glyoxime4

recently,

CH3 'C-O R O-C CHb 'Cb' )CrN'L'R=C'

CHz

Cp

CR/C\\N/L\Ns\

and,

bis(salicylaldehyde)ethylendiimine

chelates

0/H\ i ii\C/ CH=\C/' \R/

(A)

metallorganic of and

the

charge

cobalt

behaviour

of

formal

oxidation

states

and

photochemical strong

group.

4005

on

the

the

Co(III),

of

the

due

planar above

Co(I1)

at the

with

be

atom,

in the

complexes

reactions

similarities

can

cobalt

d-orbitals

redox

out 1,697

derivatives

and

cobaltcomplexes

4006

No.41

On the lacking

in the

complex

ion

other

hand

assumed

some

model

(organometallLc

properties

complexes: cation)

of

and

the

the the

e.g.

Vit.Ea4

coenzyme'were

positive

solubility

charge

of

still

the

in water.

R co+ N P

We having

succeeded

both

propane

the

above

1,3=(DOH)zpn This

are

pyramidal

I,

CoX,

(X&l,

Br,

at room correctly

are

diamagnetic,

By reaction Analyses

and

\(WH)(DO)p

cm2).

With

I)

is

appropriate

the

ed with

The

the

complexes

perchlorate

is

bound anion,

atom

forming

analyse

with

NHa,

supposed

while

probably

the

to

have

other

tetragonal

NaClO4

reaction aqueous

Grignard

water

X=Br

(A

NaC104.

[RCO(III)((DOR)(DO)~~JR~O]C~O~

(Iv)

in water-ethanol complexes

acetone,

soluble

diamagnetic

are

(II)

in

and and

= 227

I

(III)

(III)

by

orange-yellow

(R=cH*,

but

complexes with

the

(&=223,

The insoluble are formulas

AIII=232

give

ohm-'cm2).

obtained

results

are

(I).

CHICLE

agreement

reaction

in tetrahydrofurane.

crystalline, Analytical

crystalline

alcohol,

(II)

are

reagent

mixture,

in

both

(DOH)npn

[Co(III){(DOH)(DO)pn)X4~

conductivity

n ) L4 ] XI when

with

, green

for

soluble

molar

aqueous

reacted

temperature

~)rganometallio derivatives

of

complexes

bis(diacety-lmonoxime-imino)-

to obtain

ionically

nickel

[co(III)~(DOH)(DO)pn]L4](ClO4)r

with

organo-cobalt

ligand.

SCN)9.

with

the

adopting

prepared

Br,

to

which

in water.

Ohm

by

of novel

configurations.

complexes

LCo!:II)

first

structure

or water-acetone

formed.

was

coordinated

When

obtained

requirements

(X=C104,

aquara Rlnnar

anions

preparation

as tetradentate

ligand

Ni \(DOH)(DO)pn)X a

in the

are

After complexes

correct

~4~5).

of

for

(I)

(X=Br)

hydrolysis are

precipitat-

No.41

4007

aqueous

With corm. obtained

from

diamagnetic

the

and

KI

Grignard

soluble

the

complexes

reaction

mixture.

in water

Electrophoresis

( A

confirms

The

86

Iv=

the

@Co((DOH)(DO)pn)I] complexes

(V) are

(IV)

and

(V) are

ohm-'cm').

presence

or

the

organocobalt

orange-yellow

insoluble

complex

cation. By treatment [RCo

I (DOH)(DO)pn}HzO]

(IV)

and

the

NaB(CeHs)r

B(C 6H 5 ) 4 are

the

precipitated

above

complexes

halide.

The

analogy

with

(I) with

intermediate the

complexes

organowtnlllo NaBHI

in the

ethylendiamine

formation

of

a Co(I)

reaction

of

the

parallel

aqueous

solutions

of

obtained of

also

the

reduction

appropriate

derivative 1

is

cobaloximes

and

by

and

alkyl

assumed of

by

the

Co(III)bis(salicylaldehyde)-

637 .

complexes.

Stereochemistry

of

the

present

complexes

and

(V)

are

first

is being

studied

by

investigations. Complexes

soluble

are

presence

Co(III)bis(acetylacetone)ethylendiamine

I FsY

from

salts

(V). The

of

with

(IV)

organocobalt

compounds

the

besides

examples

Vit.Bap

of

coenxyme

stable

and

the

water alkyl-

cobalamins.

References

1. G.N.Schrauzer

and

J.Kohnle,

G.N.Schrauzer,R.J.Windgassen

Chem.Ber. and

G.N.Schrauzer

and

R.J.Windgassen,

G.N.Schrauzer

and

R.J.Windgassen,

2. G.Costa,

G.Mestroni,G.Tauzher

'99, 3056

J.Kohnle, ibid.

(1964)

602

22,

L.Stefani,

(1965)

(1966)

J.Am.Chem.Soc. and

332:

ibid.!!,

Ei,

3738

(1966).

J.Organometal.Chem.

6,181 =

(1966). 3. G.Costa,G.Mestroni 4. E.Frasson, =13,

893

K.S.Viswanathan

and and

Acta

toll.,

Hall,

R.N.Kunchur,

Englewood

and

G.Mestroni,

7. G.Costa

and

G.Mestroni,

9. E.Uhlig

J.Organometal.Chem.

R.Calvin,

6. G.Costa

8. R.Bonnet,

L.Stefani, and

Cryst.

12, ==

1, 201,

493

1027

(1967

).

(1959)

(1960)

5. A.E.Martell Prentice

and

C.Panattoni

Chem.Rev.z, and

M.Friedrich,

ibid.

"Chemistry Cliffs,

of

the

675

(1961).

Metal

4th

Ed.,

Tetrahedron

Letters

Tetrahedron

Letters

573

N.J.,

'2,

Chelate

Compounds",

1959,

p.266.

19, ==

1783

(1967).

19 =='

1781

(1967).

(1963).

i?.Anorg.Allgem.Chem.

343,

229

(1966).