Organolanthanides

:

103

-..._ -: . I . Y._JourniJ~fOawwmetdEcChemi.&, ~35(1977)109-&4 :~Else&rSeqiokS_A..Laussnn e+E%inkdinTheNetherlsnds

--

:

CR&Ol%NTHAN?DES I. G.

-.

..

BT~~POLYFLUOROPI-LE~~~~TTTTERB~UM 3. Deacon,

Chemistry

W.

D.

Department,

Raverty,** Monash

COMPOUNDS*

and D.

G. Vince***

University,

Clayton,

Victoria

3168

(Australia) (Received

Xay

5th,

1977)

summary Bis (pentafluorophenyl)ytterbium phenyl)mercury isolated

as the highly air-sensitive, which yielded

(cgF512yb@q. NMR,

IR, and UV&is

complex sirnil&

spectra

thermally

pentafluarobenzene

of the complex

manner and was identified satisfactory

analytical

complex

on acidolysis,

are discussed.

too rapidly

A tetrahydrofuran

spectroscopically,

thermal instability

characterization.

Reaction

for isolation.

Ytterbium metal failed

diphenylmercury

or bis (pentachlorophenylfmercti_

*

Preliminary

Communication,

**

Present

***

Present address:

address:

The “F

has been prepared

ytterbium and bis (2,3,4,5-tetrafluorophenyl)mercury ,

decomposed

of bis (pentafluoro-

(IXIF) , has been

unstable

of bis (2,3,5,6-tetrafluorophenylj ytterbium

preventing between

, pre_pared from reaction

with ytterbium metal in tetrahydrofuran

Ref.

in a

was observed but the product to react with

[ 13

Research. School-of Chemistry, University, Canberra, A.C.T.

Australian National 2600 (Australia).

Central Research Laboratories, ICI (.Au.stralia) Ltd., Ascot Vale, Victoria 3032 (Australia).

104 Introduction

:

Despite metallic

considerable

chemistry Thus,

limited.

re_ported except fluorocarbon c-bonded related end

[Z-q

in the preliminary

actinfde

ligands

, and species

(bl = Lanthanide)

Li2U (CH2SiMe3)

complexes

species

There are few of I’l-C6HS or

(I)-CSH6)3MR

(M = U or Th) [ 73 Exceptions

[ 4,s ,121 are predominant. Pr, Lu,

or Yb) [ 13,141 and

Ln = Sm or Yb) [ 161 .

and actinide

organometallics

and organo-alkali

of RLnI species

We now report syntheses

crganolanthanides

[ 1 Sl ,

Synthetic

are largely

metal reagents

from the elements

..

, and only one

by attachment

[Z-6)

, apart

and the organic

of polyfluorophenylytterbtium

and the first use of the transmetailation

compounds,

is still quite

(ll-C6H5)3UC6F5.~

(Ln = La,

organo-

have been‘

of this study [l]

of the type RLnI (e.g.

from direct syntheses

Results

derivatives lanthanides

of the type

Li[ R4Ln]

lanthanide

to use of Grignard

[16] .

and actinide

6 (tmed) 7 (tmed = N SN ,N’ ,N’-tetramethylethylenediamine)

routes to o-bonded

iodides

account

that are not stabilfsed

[Z-6]

the anionic

restricted

of o-bonded

is known [ 7J , viz.

derivatives

and solution

, knowledge

in lanthanide

no pre_parations of fluorocarbon

(q-C5Eii5)2MR

include

recent activity

reaction

as a route to

_

and Discussion

preoaration.

Isolation,

and Properties

of Bis (nentafluorophenyl)tetrakis

(tetra-

h ydrofuran) ytterbium (II)

On stirring ytterbium metal and bis (pentafluorophenyl)mercurry hydrofuran oxygen,

(!XIF) at room temperature

an exothermic

reaction

bis (pentafluorophenyl)ytterbium R = C,F6]

. R2Hg

f

pure crystals

ytterbium(H)

were obtained

decomposing

sensitive

>

[reaction

R = G6F5] .

f

THF

solution

Hg

ether and cooling.

and moisture,

(1) ,

(1) -

The

and is thermally

under nitrogen at room

of the compound in tetrahydrofuran

as the sole major organic

>

of

tetrakis (tetrahydrofuran)

or more slowly

Acidolysis

gave pentafluorobenzene

2830

R2Yb +

to oxygen

in tetra-

of moisture and

of mercury metal [reaction

of petroleum

on mild heating

under nitrogen

R2Yb f

an orange

and a precipitate

on addition

(see Experimental).

(2);

giving

exclusion

of bis (pentafluorophenyl)

compound is exceptionally unstable,

occurred

THF

Yb

Analytically

temperature

with rigorous

.2RH+

2H20tYb

2+.

product

(2)

The &n&unt of pentafluorobenzene o&g

to the presence

detected

by l-‘F NMR

~analytkal.ly showed

of traces

differed

of iocai heating

attributable

Addition

bis (polyfluorophenyl)lant.hanides The presence

probably

derived

species.

of acid directly

and subsequent

arenes

but probably

a phenomenon

with 71-C5H5Fe(CO)2-

previously [ 181 .

hydrogen observed

Samples

from the IgF NMR

NMR chemical

from of polyfluoro-

impurities

-

of 2,3,5,6-

partial

bromide

[ 2 0] , and,

derivatives,

e.g.

covalent

character

Confirmation

in tetrahydrofuran

pentafluorophenylorganometallics,

(II) complexes

metal carbonyl

ytterbium bonds.

abstraction in reactions

shifts of (C6F5)2Yb(THF)4

[ 17j of a-bonded

at least

The origin of this

of bis (pentafluorophenyl)

negligible

those of pentafluorophenylmagnesium

suggesting

Acidolysis

_

pentafluorophenylplatinum transition

involves

(1) contained

tetrafluorophenyl-mercurials

similar to those

paralleled

of (C F ) Yb@HF)4 gave not only pentafluorobenzene, 6 52 (ca. 5%) of 1,2,4,5-tetraflucrobenzene, which was

merclrry used in reaction

particular

in competition

ruled out.

for such an impurity was obtained

is not clear,

The “F

of

which might have

spectrum of impure (C6F5) 2Yb(‘l?HF)4 (see Experimental).

tetrahydrofuran,

to crystals

acidolysis

[ 17j , was definitely

because

from an impurity of a 2,3,5,6-tetrafluorophenylytterbium

Evidence

species

(below) fluorocarbon

of the organolanthanide

of 2H-nonafluorobiphenyl,

that of pentafluorophenyllithium

but also a low yield

the unidentified

induced thermal decomposition

been formed if thermal decomposition

of an impure sample

which was

ytterbium in tetrahydrofuran

to impurities,

thermal decomposition

on acidolysis.

with acidolysis.

fluorocarbon

for (2)

Since the IgF NMR spectrum of

pure .bis (pentafluoroihenyl)

may be formed by slight

from that expe-ted

of an unidentified

spectroscopy,

-no.resonances

slightly

and in

[ 191 , some planar

more surprisingly,

C6F5Fe (CO) 2 WC5H5)

some

I:211 ,

in the pentafluorophenyl-

of the analytically

established

provided

spectrum,

with the expected diamagnetism of ytterbium (II) compounds 19 By contrast, F chemical shifts for the paramagnetic

in the lgF NMR

consistent

Wb2+ , 414). (;l-C5H5)3UC6F5

are observed

from CFC13,

phenylorganometallics

(CGFs)2Yb@THF),

was

[fl/1-at 152.4,

substantially [ 17j .

displaced

Detailed

not possible

of the meta and para fluorines. analyses

of broaderzing or shifts

oxidation.

state of 11 was

upfield

by the l=ck

are

162.8,

from values

analysis

because

and 179.2 p.p.m.

for mcst pentafluoro19 of the F NMR spectrum of

of overlap

The same difficulty

between

the multiplets

has previously

of the s_pectra of .o’rfrer pentafluorophenyl-organometallics

precl-rlded [ 20,221 _

106

However,

using data from analysis

[ (?zt3P)2Pd(C6F5)Cl] appearance

as an initial

of the ortho-fluorine

19

[ 201 of the

basis,

F. NMR spectrum of trans-

computer-simulation

multiplet

of the general

was -partly achieved.

Some

unexplained

features in the experimentally observed multiplet could possibly 171 19 71 F satellites Yb, 14.31% abundance, has spin be attributed to Yb(’ 173 Yb, 16.13% abundance, l/Z; other major isotopes have spin 0, except for spin 5/Z [ 231) with JNb-2-F)

ca.

12 0 Hz,

though the. assignment

is very

tentative. Comparison

of the infra-red

tetrahydrofuran

complexes

(C6F5)31n(THP),

spectrum of (C6F5)2Yb@HF)4

with those of

[ 243 , pentaEluorophenyiorganometallics

[ 261 enabled

[ 2.51 and

most C6F5 and THF absor_ptions to be

at (F&_perimental Section) _ Intense fluorocarbon absorptions -1 [ 251 to modes v5 (al) and v 25 b*’ 1036 and 920 cm , which can be assigned

distinguished

(involving

carbon-fluorine

lower frequencies (ca.

1080-1050

fro-m partial

stretching)

than in previously and 980-945

ionic character

cm-l

(this work) by comparison

G-X stretching, at 885 cm

-1

Ring stretching

is normally

arising

Apart from

of v6 (al)

and vi26(b2) ap_pear to

F assigned straightforwardly 6-5’ [ 7J with those of other (Ii-C5H5)3UR

[17) .

For

‘&is mode may give rise to a prominent shoulder at 837 cm -1 modes of tetrahydrofuran at 1070 and 912 cm are shifted to

on coordination.

Metal-oxygen

of transition

as expected

in iC6F5)2Yb@HF),,

stretching

frequencies

metals and alkylalumi;lium

in the range 500-350 cm -’ to assign

) , possibly

mode of C F derivatives, v6 (cl), involving 65X observed at ca. 500-750 cm -1 117,25,27l, e.g.

(I 013 and 876 cm-I)

unable

compounds

of (I)-C5H5)3UC

lower frequencies

reported

[ 7,25,27]

for C6F5C1 and 806 cm -1 for (C6F5)2Hg

(C6Pj)2YbWP)4,

complexes

values

of the spectrum

An ‘X-sensitive’

complexes.

respectively

reported

(10.50 and 94.6 cm-‘)

be those

are at significantly

re_ported pentafluorophenyl

in the C6F5 - Yb bonds.

I the lowest

G6P5) 2yb @I=),

of the C6F5Yb group,

[28]

[ 241

of tetrahydrofuran

compounds

have been

, though other authors have been

them owing to marked speotral

differences

between

closely

related

complexes [29] . A medium intensity band of (C6F5) 2Yb@HP)4 at -1 463 cm is not readily assigned to a mode of the C6F5 group or the TH!? Sigand,

and could arise

The colour

of the

from ytterbium-oxygen

complex

500 nm, and the similarity

derives

of the spectra

(Nujol mull) and in te’kahydrofuran change

on dissolution.

where absorption

for the complex

is consistent

No absorption

characteristic

stretching.

from three bands in the region in the solid

with negligible

350state

structural

could be detected near 1000 nm, 2 viz. 2F F7/2 S/2‘

of ytterbium (III),

-1

is

.

107 expected

[ 303.

oxidation

to ytterbium @II) gave rise to a weak peak at 978 run.

absorption

In confirmation,

maxima of -(C6P5)2Yb0HF)4

transitions,

since

f-+f trarmitions

for aqueous

readier

previously

been observed

ions and the energy -part of the visibie

between

ease

since

n-bonded

organolanthanides

observed

for (C6F5)2Yb(THF)d_. a detailed

the

Some correlation

has

of divalent

[ 311 .

that

from ligand

have been observed

r 12a, 321 with intensities

discussion

lanthanide

It is also likely

derives

E,

4f+5d bands

reflecting

of oxidation

of (C6F5)2Yb(‘EIF)4

such transitions

is attributable

band at 352 nm (log

All the possible

compound.

of their 4f+Sd transitions absorption

charge transfer,

Although

[ 311 .

are known,

In addition,

part of the absorption

are at lower energy than that of YbC12,

oxiciation of the organometallic

from intraligand

[26] .

give a broad diffuse

ytterbium (II) chloride

of (C6F5)2Yb6HF),

is colourless

At least

since these

to arise

partial

The

C6F5 and THF complexes

(C6F5)31n@HF)2

are impossible.

to 4f-Gd transitions,

of a trace of air to allow

are unlikely

numerous colourless

and the mixed s_pecies

2.71)

admission

+ metal

for both o- and

similar

to those

of the structure of the complex

or of the

- Yb bonding would be premature, a brief comment on the bonding is C6F5 possible_ The successful isolation of (C6F5)2Yb@HP)4 and its moderate stability isolate above

in tetrahydrofuran

at room temperature

pentafluorophenyllithium

-1 O” [ 17j * can be atttbuted

C6F5 - Yb bonds.

Significant

NMR data (above!.

Crystals

been obtained,

compared

with the failure

and its ready decomposition to greater

covalent suitable

and in any case

covalent

character for X-ray

actue handling

in diethyl

character

is also

problems

in the

suggested

crystallography

to

ether

by 19F

have not yet

could well

preclude

use of this technique. Attempted Prenaration

and Isolation

of Other Diorganoytterbium

Bis (2,3,5,6-tetrafluorophenyl)ytterbium metallation sensitiva

[reaction crystals.

satisfactory

*

analytical

(1);

R = R-HC6F,j

However,

philic

ether.

C6F5Li

chloride

is more likely

appears

less

and was isolated

and decomposition

is significantly

Polyfluorophenyllithium

in THF than in ether [ 333 , hence

displacement

stable

been prepared as orange

the compound was too thermally

characterization,

There is no reason to believe

than in diethyl

has also

compounds

by transair-

unstable

products

more stable

self-decom_position

in the former.

Compounds

were

in THP

are more nucleoby nucleophilic

Pentafluorophenylmagnesium

in THF than in ether [ 343 .

for

108

visible

1,2,4,

in the crystals.

[reaction

(2);

after this reaction

was -ca .l.

tetrahydrofuran Intense

Experimental).

?rom their positions

between

v&h

spectrum showed

fluorocarbon

Jresumably

reaction

coilld be induced between

and Mechanistic

organolanthanides,

was also

observed

and no complex

Comments

conversion

Reaction

formed orange solution,

c

+

4

is accelerated

hence the transition

-

No reaction

chlorophenyi)mercury

been used to give o-bonded

Conceptually

.

temperatures severe

related

Transmetallation

by

reactions

agR2

are

or no solvent,

as in (1).

Recent

proceed via metal-metal

bonded

e.g.

RYbRgR d

withdrawing

R2Yb +

substituents

state for the rate determining

to react is probably

can

path for (1) is:

L

carbanionic

reactions

with a hydrocarbon

conditions,

a possible

by electron

(see [40] ) , has considerable

in tetrahycirofuran

could be isolated.

attempts to obtain phenyllanthanides

*&at the latter class

Accordingly,

Yb

turned brown

(7-C II ) by ytterbium metal into 5 5 3 y (y = 1 or 2) I3fl , and the reduction of mercuric

under less

[LiO] suggest

R2Hg

S-tetra-

of ClHgCr(C0)

either at elevated

intermediates.

bis (2,3,4,

rapidly

have not previously

but unsuccessful

in polar solvents

studies

impurities.

on Transmetallation

iodide by samarium metal giving SmI7 F39] _

s

suggests

A1 ‘F NMR

ytterbium and either bis (pentachloropheny1)mercur-y

reactions

ClYb[Cr(CO)3(8-CgH5)]

be effected

Section)

of paramagnetic

between

but the initially

this method have been reported [ 37,381 viz.

The

in tetiahydrofuran.

Transmetallation

known,

are lowered

and structures.

of bis (2,3,4,5-tetrafluorophenyl)ytterbium,

or ciiphenylmercury General

(Experimental

owing to the presence

and ytterbium,

owing to thermal decomposition,

-1

spectrum of a mull of the tetrafluoro-

have similar compositions

spectrum could not be obtained

of

group (see

bands of (C6F5)2Yb(I’HF)4.

phenyl compound and that of (CsF_Q2Yb~HF)4

fluorophenyl)mercury

indicative

2,3,5,6-tetrafluorophenylorganometallics

for corresponding

A transmetallation

features

of the product as

bands at 1200-850 cm

the ultraviolet/visible

that the compounds

formulation

and of a 2,3,5,6-tetrafluorophenyl

for reported

[ 35,361 , as observed similarity

8, consistent

The ix-&a-red

<@-IC6F4)2Yb. coordinated

was formed on acidolysis 2t determined , and the ratio moles RI-I/moles Yb

R = R-HC6F4]

S-Tetrafluorobenzene

step,

character.

(C6F5 z+-

Ph) ,

p_Tesumably (4) The failure of bis(penta-

due to insolubility

and is not mechanistically

Iig

significant.

of the mercurial

109

Excnhnental Reagents

and Manipulative

Koch-Light.

reported-methods

1,2,4,

[ 35,41,42]

S-tetrafluorobenzene

fluorobiphenyl passage

Ytterbium powder was obtained

Tcchnfques:

Bis (polyfluorophenyl)mercurials Authentic

.

were prepared samples

by Dr. A. G. Massey.

through columns of oxygen removing

molecular

sieves

distilled

(Union Carbide

from calcium

Light petroleum

(b.p.

Nitrogen

catalyst

and

2H-nona-

was purified

by

(IW9F R3/11) and was refluxed

over and

hydride then lithium aluminium hydride under nitrogen. 60-80°)

and diethyl

from sodium then lithium aluminium stored under purified

Authentic

.

Tetrahydrofuran

13X).

by

of pentafluorobenzene

were from Bristol Organics

was provided

from

and purified

ether were refluxed

Solvents

hydride under nitrogen.

Reactions

nitrogen.

over and distilled

were carried

were

out in Schlenk glass-

ware,

which had been heated at 120° and purged of air by at least three -2 mm)/nitrogen cycles _ Solvents were added by successive evacuation (IO syringe

techniques

and it was

immediately

after removal

manipulated

in recirculating

HE43-2/HE93Bor Organic Analyses:

GSIXO,

Microanalyses

Melbourne, in sealed

dry boxes

constructed Melbourne)

were

(Vacuum Atmospheres

box ofthe Division ofApplied .

were by the Australian

the air-sensitive

punctured rubber tubing

Solid complexes

needles.

atmosphere

a specially

Chemistry,

important to replace

of syringe

Microanalytical

Laboratory,

compound being submitted as weighed Ytterbium was determined

aluminium capsules.

the complexes

by titration with sodium ethylenediaminetetraacetate

xylenol

orange

indicator,

acetate

[43] .

the solution

Pentafluorobenzene

being buffered

and 1,2,4,

samples

after acidolysis

of

using

at pH 4.5 by sodium

S-tetrafluorobenzene

were

determined

quantitatively by ultraviolet spectroscopy. 19 Instrumentation: F NMR s_pectra were obtained with Varian A56/6OA or Bruker WH-90 external

instruments _

CFC13.

immediately

Hexachlorobutadiene

dissolved

Infra-red

with Perkin-Elmer

the compounds.

spectra

Ultra-violet/visible

since

spectra

were obtained

Quantitative

out with Varian Techtron

upfield

from

were reccrded

compounds

as Nufol

mulls

521, 577, or 257 spectrophotometers.

could not be used,

in tetrahydrofuran

spectrophotometers.

shifts are in p.p.m.

Spectra of the ytterbium compounds

on dissolution.

were recorded

Chemical

immediately

of compounds

with Gary

fluorocarbon

335 or Unicam

it reacted

as Nujol

with mulls or

17, or Unicam SP8OOA

determinations

SP8OOA instruments.

were carried

110

Preoaration of Bis (Dentafluorophenyljtetrakis Ytterbium

powder

yellow-green,

giving

a deep orange-red

filtration petrol

was cooled compound,

0.70 g,

{with explosion:

darkens

at 754

furanj :

108.3

21.8;

(Pound:

C,

in addition to the foregoing 1626s,

cm-l):

but detectable), 1067m-s,

H,

(i)

in tetrahydrofuran, as a Nujol

air,

a weak absorption

intense

giving

bright orangeeither by

were washed

with

under nitrogen,

41.9; C

H,

3.9;

Yb,

78O 21.6.

H

F 0 Yb calcd.: C, I9 28 32 10 4 F NMR spectrum (tetrahydro-

(complex m, 3F, F 3,4,5) 3-8;

Yb,

21.1%)

showedweak

(F ortho to H [ 35,421)

Infra-red

absorption

1460s (coincident

1244w,

p.p.m.

1219s,

1179m,

with Nujol, 1139w,

(ix),

E

2.76),

,

in pure tetrahydrofuran acid

the crystals

as heating (ca.

caused

0.25 g;

and 444 (2.74) nm.

After a brief exposure

at 978 run.

at room temperature,

(300-l 000 nii):

399 (2.73),

455~480vbr.

was observed

sample

On being

turned black,

a similar accurately

(ca.

The reaction

collected

quantitatively

5 ml,

0.2-0.3

M) precooled

mixture was distilled (a control

experiment

to

stored for 48 hr. attributable

colour change. weighed)

(8 mlj under nitrogen and was cooled

syringe _

837sh.

and the others to the pentafluorophenyl absorption

373, 405sh,

A weighed

dilute sulphuric

C,

multiplets.

1295s,

370 (log

mull,

to thermal decomposition, Ucidolysis:

to S-8 ml

985w, 950sh, 920~s (br), mvs (br), -1 . 570m, and 463m cm Frequencies underlined are

(ii)

under nitrogen

at -20°

(P ortho to Yb) and 139.1

Ultraviolet/tisible

[25,27j.

was concen*zated

temp.

42.0%).

~attributable [ 243 to tetrahydrofuran group

dec.

43.9%.

40.0:

14IO.s. 1360sh,

(br),

through a celite

These were collected

1595m, 15131~1,ca.

IO36 and 1013~s

709m, mm

overnight

(Pound:

44.4,

C6F5,

centred at 114.5

(1700-400

29%),

(m, ZF, F 2,6j and 161.4

An impure sample multiplets

below),

Yb,

for 4 hr.

and were dried under vacuum for 2-3 min at

(yield,

I-I, 4.1;

and mercury was deposited.

of the mother liquor by syringe,

(2 ml) and ether (2 ml),

42.3;

The filtrate

of the required

(by acidolysis,

the mixture became

Petroleum ether was then added until turbidity

room temperature

C6F5

min.),

which was then filtered

mercury.

under vacuum.

or by removal

(I-2

commenced,

and the solution

red c_~stals

period

(I O”j and stirring was continued

solution,

pad to remove precipitated

appeared,

reaction

mixture was cooled

by evaporation

(10 ml) were stirred under nitrogen _at

an induction

After

an exothermic

The reaction

ytterbium (II) (IX) _

(0.581 g, 3.36 mmol) and bis (pentafluoropheny1)mercui-y

I:1-61 g , 3.00 mmolj in tetrahydrofuran room temperature.

(tetrahydrofuranj

was

to O”.

dissolved Degassed

to O” was added by

and pent&f.Luorobenzene gave a recovery

was

of 98.0%)

together

&ith tetrabydrofuran

terminated

in a cooled

when the boiling

was diluted

quantitatively

determination

point remained with rectified

white spirit before

was

The distillate

at 1 OO” for IO min.

The ultraviolet

of the fluorocarbon.

The distillation

(O”) vessel.

spectrophotometric

spectrum of the diluted

distillate was identical with that of,authentic pentafiuorobenzene, whilst 19 F NMR spectrum of a typical undiluted distillate showed the resonances expected

for pentafluorcbenzene

features

at 133,

158,and

biphenyl

to the solution

of the additional

fluorine

but also a sharp triplet spectrum of an authentic

in a reaction

of an analytically

indicative

(see above)

and the above (comparison

to crystals

Addition

of (C6F5)2Yb@HF),

and a black product typical

violence,

rather than the acidolysis

impurity,

with the

of 1,2,4,5-tetrafluorobenzene.

acid directly

was obtained

impure sample

of pentafluorobenzene

sample)

of explosive

decomposition

2H-nonafluoro-

that this compound was not the source I9 F IWlR spectrum of the fluoroThe resonances.

at 139.4 p.p.m.

sulphuric

very weak broad

of authentic

established

not only the resonances

of degassed

with additional

Addition

167 p.p.m-

carbon product from acidolysis showed

together

the

resulted of thermal

product,

white

ytterbium (II) sulphate.

The Tetrahycirofuran Reaction

Comulex

of ytterbium powder

out using

conditions

bis (pentafluorophenyl) precipitation

(containing

complex

of bis (2,3,5,

calculated

as

specks

isolation

substantially

of discoloured

@HF)J

from calculated

3095w (w(CH) ofg-HC6F4

values]

[35],

1347w,

1292m, mm,*l217w,

96O*v,

907s,

values

.

1644w, xsh,

854 and 844~s (br), underlined

are attributable

solid)

[Found:

absolute

815w,

are attributable

procedure

of an impure tetrahydrofuran [yield,

p-HC6F4/‘Yb for % Yb,

Infra-red

0.52 g, 46%, ratio

absorption 1494s (br),

1137~s

(br),

742s.

(determined

% HC6F4 differed

1585s,

[24]

or rapid

by petrol gave orange-red

Gtetrafluoropheny?)ytterbium

, 1.8;

(I 0 ml) was

those for the preparation of

A similar

ytterbium.

(E-HC~F~)~Y~

acidolysis)

Frequencies

similar to

of the product from tetrahydrofuran

crystals

foliowing

(0.486 g, 2 _ 81 mmol) with bis (2,3,5,6-

(1. 01 g, 2.02 mmol) in tetrahydrofuran

tetrafluorophenyl)mercury carried

of Bis (2,3,5,6-tetrafluorouhenyl)vtterbium.

(4000-650 ca.

lllOw,

cm -l):

141Ovs,

1062~

1022vs, ’ -1 and 678 and 668~s cm .

to tetrahydrofuran

[ 3.5, 361 to the 2,3,5,6-tetrafluorophenyl

and the others

group.

Ultraviolet./

visible absorption (Nufol mull; 300-700 nm): 391 and 480 nm. Satisfactory 19 F NMR and ?MR spectra could not be obtained, probably owing to paramagnetic impurities.

The compound

slowly

turned brown

(4-48 hr. depending

on the

112 sample)

on standing

at room temperature,

presumably

owing to thermal.

.-

’

instability. Acldolysis:

Cleavage

of

fluorocarbon

product,

identified

and “F

the compkx rvit!~ acid and determination of the

NMR spectroscopy,

Direct addition decomposition

as I ,2,4,5-tetrafluorobenzene-

was carried

of acid to crystals into a black

by ultraviolet

out as for (C6F5f2YbCfHF)4

of the complex

resulted

..

(above) 1

in violent

solid.

Other Reactions (i)

Reaction

ytterbium

of bis (2,3,4,5-tetrafluorophenyl)mercury

(6.46 mmol) in tetrahydrofuran

precipitate

of mercury and,

turned brown indicative crystallized (ii)

initially,

an orange-red

at 0-30°

solution,

gave a

which rapidly

No complex

could be

from solution.

in tetrahydrofuran at 55-60°

(1.73 mmol) and ytterbium

(13 ml) were stirred overnight

for 3 hrs,

no reaction

Diphenylmercuq

and no reaction

(1.79 mmol)

at room temperature,

and

being observed.

(1 _ 78 mmol) and ytterbium

furan (12 ml) were stilled 2 hrs,

(10 ml) for 5 hrs.

of thermal decomposition.

Bis (pentachloropheny1)mercui-y

(iii)

(3.00 mmol) with

overnight

(1.90 mmol) in tetrahydro-

at room temperature

then under reflux for

was observed.

Acknowledgement We are grateful Dr.

N.

Ham,

simulation

CSIRO Division

of the bIR

Dr. P. C. Wailes Chemistry, University

to the Australian

Research

of Chemical

spectrum,

Physics,

Dr. A, J. Koplick

and Dr. H. Weigold.

for-assistance

Grants Committee

of Applied

Organic

and Dr. A. G. Massey,

for a sample

Loughborough

out the

for ex_perimental assistance,

CSIRO Division

with dry box facilities,

of Technology,

for carrying

for support,

of 2H-nonafluorobiphenyl,

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