On the indenyl compounds of actinide elements Part IV: Preparation and properties of the trisindenyl thorium tetrahydroborate

INORG. NUCL. CHEM. LETTERS Vol.14, pp. 393-403, 1978. Pergamon Press. Printed in Great Brita~

ON

Part

IV

THE

INDENYL

COMPOUNDS

: Preparation

and

OF

ACTINIDE

properties

of

ELEMENTS

the

trisindenyl

thorium

tetrahydroborate

J.

GOFFART

G.

MICHEL,

B.P.

Laboratory University

of of

B-4000

(R~3ceived

July

iO

GILBERT

and

G.

DUYCKAERTS

Radiochemistry

Liege, LIEGE

Sart

Tilman

(Belgium)

received for p~blication 3 August

1978;

1978)

ABSTRACT. The thorium

preparation

and

the

tetrahydroborate,

spectroscopy

has

(n5C9H7) 3ThBH4

allowed

hydrogen-bridged

characterization

to

metal-BH 4

assign

to

is

this

of

trisindenyl

reported. new

Vibrational

compound

a tridentate

structure.

INTRODUCTION. Interest ~ctinide

in

elements

(1,2) . H o w e v e r 3f

these

metals

~everal i.-

up

types

of

Ionic

bonding

metal

to

the

the

chemistry

has

expanded

to

(I,

Raman

symmetry

C.largQ

de

3-5)

spectra

the

organometallic

limited.

transfer

group. in

on

within

compounds past

few

of years

tetrahydroborates

Tetrahydroborate

can

adopt

:

"involves BH4

organometallic

rapidly

data are

bonding

tetrahydroborate and

now,

of

Several

these

have

of

one

electron

investigations

compounds

accordingly

and been

from of

assignments made

based

the

alkali of upon

metal

infrared the

Td

(4).

Recherches

~ l'Institut

Interuniversitaire

Nucl4aires.

393

des

Sciences

394

Indenyl Compounds of Actinide Elements

2.-

As

shown

metal two

by

via

or

structural

three

three

However

we

the

(Me-H-B)

bonds.

center

hydrogen

must

coordination

studies,

point

bridge out

bonds

that

configurations

BH 4 i o n

have

also

Geometries

have

only

can

been

having

observed

bidentate

been

bind

and

identified

to

a

one,

(4,5).

tridentate for

covalent

com-

pounds. 3.-

The

tetrahydroborate

a polymer

In ward of

bond,

for

structure

general,

method

ligand

of

locating

vibrational

classical

hydrogen

also

spectroscopy capable

X-ray

were

air-

atoms

carried

nitrogen.

The

atmosphere chloride

out

and in

near

solvents

heavy

mM

of

solid

refluxing was in

in

150

N a B H 4.

to

The

sublimated

product

the

yield

is

leads low

prior

to

methods

metals

atoms

in

and

use.

compounds, under

i0

reaction

was

mixture days.

and

the

After

mM

of

were

stirred this

10-4torr)

and

extracted

again

purification. an

argon

pure

(~5C9H7)3ThCI

treated and

time,

10 d a y s

giving

an

with

with

This

mixture evaporated

pentane,

of

weight

by

cryoscopy

Molecular

weight

by

mass

in

benzene

spectroscopy

: 600

: 592

±

12

(theor.

; purifi-

spectrum

fluorescence.

Molecular

under

n-pentane.

method

Raman

I0

heated

the was

by

oxygen-sensitive

excellent

or

thorium

tetrahydrofurane

moderately

operations

(i0,Ii) .

extracted

a product

types

suitable

argon

under

described

(THF)

I0

all

Tris(n5-indenyl)

tetrahydrofurane

% after

not

purified

distilled

previously

pale-yellow,

these

SECTION.

tetrahydroborate

NaCI

a straightfor-

(9).

was

88

metal

are

residue

is

high, to

as

during

remove

(150°C,

final

very

The

yellow

The

cation

of

conditions

filtered vacuo.

dried

thorium ml

link

distinguishing

glove-box

were

synthesized

Tris-(n5-indenyl) dissolved

special

immediately was

of

moisture-sensitive

a

to

provides

diffraction

EXPERIMENTAL Having

known

(6-8).

investigation

since

is

592,35)

with

Indenyl Compounds of A c t i n i d e Elements

% Thex p An

: 39,2

attempt

only

; % Ththeor.

to

prepare

identified

analysis,

and

was

thorium

prepared

study

that

used

this

for

its

BH 4

was

counterpart

cryoscopy

Molecular

weight

by

mass

infrared-

no

deuteration

; % Ththeor. and

NMR

on

of

the

infrared

spectra

organic

hexachlorobutadiene 4000-200 The

c m -I

infrared

polythen The in

nujol

spectra

in

with

spectra

mass

spectra

data

mulae

(C9H7) 3ThBH4

cular

~as

masses,

polymerisation measurements monomeric

we in have

that

and

From

species

and

596,35) .

4 have the

shown

that

molecule.

compounds

in

KI

350-30 30

IR

cm

were

pellets

Beckman

with

can

-i

12

in

were

Fourier

recorded the

as

region

spectrophotometers) obtained

in

spectrophotometer.

spectrophotometers

described

the

clearly

new

absence

conclude gaseous

also

I)

DISCUSSION.

that

In

the

The

that

solutions.

the

case,

above

new

the

other

correspond

each

peaks

phase.

indicated

benzene

of

confirm

compounds

( C 9 H 7 ) 3 T h B D 4.

the

the

in

AND

(table

indicating

found.

to

(13,14).

tical

peak

and

FIR

obtained

RESULTS

The

complex

12

(theor.

of

thorium

region

a Polytec

were

literature

the

125,

the

%).

identical

(C9H7)3ThBD4

parts

chemical

MEASUREMENTS.

mulls

(Perkin-Elmer

pellets

Raman the

or

of

±

(~5-C9H7)3ThBD

INSTRUMENTAL

The

for

: the

).

: 598

: 596

: 38,91

spectra

occurs

benzene

%

40

BD 4

a manner

90

by

(yield

: the

in

spectroscopy

failed

characterized

(yield

in

4.

method

(12)

synthesized

by

The

same

tetradeuteroborate

weight

: 39,4

the

(C9H7) 3U.THF,

Molecular

% Thex p

(C9H7)3ThBH

infrared-spectroscopy

Tris-(~5-indenyl) for

for

(C9H7) 3UBH 4 by

product

mass-

: 39,17

395

the

to

expected

compounds

present

new

of

the

for-

molecular

the

results

analy-

moleno

cryoscopic

compounds

exist

as

.

396

Indenyl Compounds of Actinide

TABLE Partial

mass

m/e

spectra

I

(~5-C9H7)3ThBH 4 and (~5-C9H7)3ThBD 4.

of

Relative intensity

Ion

Elements

m/e

Ion

Relative intensity

592

(C9H 7) 3 T h B H 4

2.3

596

577

(C9H 7 ) 3 T h +

5.4

577

(C9H7)3ThBD ~ + (C9H7)3 Th

477

(C9H 7) 2 T h B H 4

481

(C9H7)2ThBD

462

(C9H 7 ) 2 T h +

88.6

462

(C9H7)2 Th+

362

(c9H7)ThB~

24.3

366

15.1

347

(C9H7)ThBD ~ + (C9H7)Th

100

+ 347

(C9H 7 ) T h

Inlet

temperature

150°C

Vibrational

spectra.

Solid

infrared

are

state

shown

in

obtained

a.

The

3100-2850

the

medium

C-H

vibrations,

an

and

figures

previously

weak

indication

; probe

i and for

cm

-I

bands two

of

the

1500-1300

cm

Raman 2.

other

region between

very

weak

very

temperature

spectra They

of

are

: The

basically

3100

9(C-H)

sligh~y

6.0 23.8

; E = 70

indenyl similar

region -i

3000

cm

at

2930

and

aliphatic

eV.

derivatives to

compounds

and

bands

i00 53.8

new

indenyl-actinide

1.8

~

240°C

the

1.6

those

(11,12,15,16)

contains, , due 2850

to cm

character

aromatic

-1

of

besides

giving the

indenyl

ligands.

b.

The

lines

in

the

stretching line

of

-I

vicinity

of

1475,

vibrations

of

both

(~5-C9H7)3ThBH

intensity

region

reduction

dent

Laser

light.

tric

vibration,

4 in

with The

infrared

1450

and

C 5 and

benzene

a change

behaviour

probably

: The

is

1335

cm

C 6 rings.

solution of

bands -I The

characteristic with

the

Raman

correspond 1337

undergoes

polarization

a A 1 vibration

and

an

plane of

a slight

to

cm -I

C-C

Raman

important of

the

a rather degree

incisymme-

of

deformation.

~.

The

spectrum

of

(C5H5) 4 A n

presents

a band

around

1070

cm

-i

which

Indenyl Compounds of Actinide Elements

has is

been

assigned

observed

1040

cm

-t

chloride thorium

in

all

Its (I)

(i) the

is

chloride

a C-C

is

vibration.

compounds

reduced

shifted

(II)

deformation

indenyl

intensity

and

I

to

to

975

in cm

of

actinide

tris

-i

in

397

An

infrared

elements

(l-ethylindenyl)

band

around thorium

tris(1.3bisdeuteroindenyl)

(17) .

RAMAN

4000

2000

3000

FIG. 1

1~OO

VIBRATIONAL

100(3

-1

5,O0

5 cM S P E C T R A OF (e9 C9HT)3ThBH 4

300

100

_t. )o

3600

FIG. 2

2doo

VIBRATIONAL

~oo

SPECTRA

1ooo

s~ ' 30o

cM-1

O F (~5C9H7)4"hBO,j,,

C2H5 (~)3

D thCI

(~D)3

(z) As

in

the

to

a C-C

case

~6o

thCI

(]T) of

deformation

tetracyclopentadienyl vibration

of

the

actinide, C~

ring.

we

assign

this

band

398

d. cm

Indenyl Compounds of Actinide Elements

The -i

at

800-700

exhibit

785

cm

-1

cm

bands

-1

region of

seems

: The

high

intensity.

correspond

to

tris(l-ethylindenyl)thorium tris(1.3

e.

The

gned is

strong

infrared

a vibration

found

at

the

same

actinide

studied

actinide

compounds

f.

The

and

cm

-I

at

in

of

~.

skeletal

390

of

the

cm -I

as

in

this

ment

the

only bands

around

Therefore (A 1 a n d

h.

The

borate I.

region

given

From

the

and

infrared

band

disappears to

633

cm

can

be

700

in

-I

in

(17).

440

cm

indenyl of

anion the

observed

-1

in

assi-

: this

nature

of

the

substituted

LiC9H 7

(17).

band

indenyl

It

disappears

alkali

metals

(17).

observed

we 225

region

vibrations

is

still

in

indene, This

(17).

note and

in i00

indenyl

band It

-1

absorptions

is

shifted

probably

table

number

local

symmetry

purely

ionic

of of

group

,

consider

(18). but

The

when

to

around

belongs

and

to

to

the

region

definitive compare

differing

infrared

independently

the

we

compounds

Raman

belong

of

the

spectra

one

lines

fourth

Th-C9H 7 and

assign / the

by

spectra,

below

ligand and

ligand.

C9H7-Th-C9H

7

(11

regzon

characteristic in

may

region

thorium

both cm

: We

difficult

trisindenyl

vibrations

the

the

It

shifted

KC9H 7 and

counterparts

inner

BH 4 v i b r a t i o n s

consider

of

compounds.

vibrations

these E)

is

is

around

also

intense

800

C 5 ring.

the

16)

is

NaC9H7,

actinide

different

(11,

-1

deuterated

6(C-C)

The

cm

and

independently

It

between

vibration.

band

derivatives

390

indenyl

in

very

chloride

C 6 ring

15).

and

tetrahydroindenyl

band

the

frequency

(11,

in

350

chloride

absorption

of

spectra

The

a CI-H

bisdeuteroindenyl)thorium

to

salts

infrared

: For

the

vibrations

ensuing of

the

discussion, complexed

we

shall

tetrahydro-

II. infrared the

BH4

only

bands group

two

(table

is

infrared

lower

II)

it

than

bands

Td

(T~)

is

clear

since are

that

for

a

expected.

the

Indenyl

2.

On

the

other

hand,

(~5-C9H7)3ThBH

c m -i , s h i f t e d

2485 solid

state

behaviour buted

to

as is

in

Compounds

to

1863

benzene

observed

or

in

4

c m -I

Raman

a boron-terminal

exhibits

solution

spectra.

hydrogen

and

BD4

vibration

(n5-C9H7)3ThBH4 Raman

Raman

vw

2485

m

2224

vw

2225

w

2155

w

1568

1177

s

906

vw

I

1851

I

1

w

I

I

fig 3 :INFRARED

The

same

can

be

attri-

w vw

I

solid

state.

H/D ratio

H/D ratio

Raman

Infrared

1.34

1.33

1863

m

1662

w

1 .34

1560

w

1.38

898

m

I

~ 2600

1 .31

1.31

I

rahydrofurane

i

I

2400

SPECTRA

in

3).

(cm-l) i n

Infrared

I

band

well

(4,5,19,20).

(n5-C9H7)3ThBD4

Infrared

as

at

II

frequencies

2489

1180

This

band

infrared

(figure

vibration

TABLE

BH4

an

(n 5 _ C 9 H 7 ) 3 T h B D 4

for

THF

399

of Act,..ide Elements

I 2200

OF

I

I 2000 ,~ c nT 1

(m~)-CgH7)3ThBH4j

IN SOLUTION

400

Indenyl Compounds of Actinide Elements

These the

two

cryoscopic

thesis the is

observations

of

the

known

2300

benzene

permit

In

metal

of

last

the

plexes

thorium

spectra

of

the

The

spectrum

infrared

solutions

The

also

agree

A 1 stretching

tion

is

active

doublet

rated

of

compound,

with

both

but

The

most

characteristic

the

1500-1300

but

one

band.

is

not

When

we

that

consider

compound.

In

to

It

is

rise

to

bands

structure, cm

-I

is

region, environ-

symmetry)

that

are

the

bidentate

to

of

the

to

absorption

this

and

the

scheme. tridentate

tetrahydroborate

to

in it

be

com-

in

good

a bidentate

agreement

ligation 4

in

with

geometry.

benzene

or

THF

hypothesis.

and

of

to

infrared to

is

spectra

the

not

the

could

be

probable shifted

to

however,

(fig.

2).

I et

cm -I

ligation

for

by

ratio circa we

is

deutelines

certainly

expansion

spectrum

masked H/D

vibra-

corresponding

bridge

infrared

stretching

easy.

a bidentate to

B-H t

1662-1560

spectra

the

region,

be

(~5-C9H7)3ThBH

assigned

the

should this

appear

Raman

band

observed

band

clear

correspond

observation

band,

argue

give

a C3v

not

is ~ i f t e d

the

their

cm -I

might

hypothetical rated

and

structure

molecular

do

for

as

tetrahydroborates

in

is

corresponding

Raman

in

weak

band

3)

this

cm -I

very

E

It

known

opposed

(fig.

2225-2155

(4,5).

well

the

well

analogous

2100-1600

, monodentate (A 1 a n d

compounds as

are

This

-i

bonds

of

hypo-

as

(22,23).

monodentate

of

cm

be

(AIk3B) 2H-

in

the

BH 4 g r o u p

should

depending

bonding

vibration

in

but

and

III).

new

structure

monodentate

the

derivatives

(table

The

for

bands

configurations,

(4,5,20)

(21).

in

BH 3 d e f o r m a t i o n

a tridentate

The

two

possibilities

coordination

band

discard

the

bridge,

1150-1000

exhibit

to

spectra

and

frequency

this

mass

boron-hydrogen

hydrogen

of

the

Th

(4,5), and

terminal

The

region

the

B2H;

a vibration

to

~

species

for

that

between

complexes

proposed

the

bond

polymeric

for

expected

spectra

ionic

position

5elonging

The

in

with

exact

ment.

The

measurements

cm -I.

associated

are

of

established

above

the

results

of

geometry

well

the

a purely

existence not

and

of

the

(n5-C9H7)3ThBH4

strong

(table 1000

mode.

cm

observed

II) -I no

1337

cm

-i

this

in

the

deute-

additional

,

Indenyl

Compounds

of

Actinide

Elements

..

,-I I

0 0 O~

4a o o

i.~ 0

,0 I~

i~ o

u'~

-,4

.IJ r~ 0

.,-4 o

0 O m

+

Lq

H ~ ~ ~

U)

~

-

-

~

~

~

-

~U 0

ml

4J ~

h 0 ~4

401

~ 0 O

~

+

O 'O

O 00

r-' ~1

+

H

H

Lq

I~

H

~ -

N

+

+

>

0 I to (1}

o

o

0 0

O 1.~

O O

O O

~-4 I

.-i I

0 0

0 0

Cq I O O t.0

C~l I O ~ IN

I O Lq Cq

0 0

0 u-,

0 0

fxl I 0 0

~ I 0 Ln

¢Xl

Cxl

~--i

o~

o c~ ).4 q4

0

©

0~ 0

4~

N 0

r~ 0 -,-I 4o r~

-,4

~

4.1

•

O O ~O I

I

I

O

.q N

>

ffl v

~,\I

~3

v

o A

~4 44 r~

4J 4J CN

~

\/

H

U

m

•

~

-,-t 4-) ~ m

r-, r~

~1 -IJ

402

Indenyl Compounds of Actinide Elements

band

(fig.

The

I and

strong

-i

1177

cm

in

also

deuteration bridge

2).

deformation

IR b a n d

which

Raman

active

(table

III) .

is

and

shifted

to

belongs

to

898 the

cm

-1

upon

tridentate

CONCLUSIONS. Vibrational unambiguous actinide of

spectroscopy

distinction

between

interactions.

(n5-C5H5)3AnBH4

presents

(~5-C9H7)3ThBH

of

compounds

(24,25)

in

us

analysis

It

that seems

a tridentate

solution

to

and

present

different

concluded

structure.

4 that

both

the

A previous

a bidentate

on

allows

in

a reasonable

possibilities

of

the

the

infrared

actinide

from

our

BH4-

spectra

molecule

present

structure

prevails

the

state.

solid

of

study for

this

type

ACKNOWLEDGMENTS.

Financial Nucl~aires

support

(Brussels)

Professor

J.

Fuger

also

to

express

for

want their

technical

by

is

who

Institut

gratefully

assisted

our

thanks

Interuniversitaire acknowledged.

us

by

his

to

F.

Gilnay

des

We

helpful

also

Sciences thank

comments.

and

G.

We

Lardinois

assistance.

REFERENCES.

I.

B. K A N E L L A K O P U L O S and K.W. BAGNALL, Chem., ser. O n e ~, 2 9 9 ( 1 9 7 2 ) .

2.

E.C. BAKER, G.W. HALSTEAD and K.N. RAYMOND, Bonding" 2 5 , 23 ( 1 9 7 6 ) , S p r i n g e r Verlag.

3.

H.

4.

B.D. JAMES (1970) a n d

and M.G.H. references

5.

T.J. MARKS references

and J.R. KOLB, cited therein.

6.

D.S.

GYSLING

and

MARYNICK

M.

and

TSUTSUI,

W.N.

Adv.

MTP

Organomet.

WALLBRIDGE, Prog. cited therein. Chem.

LIPSCOMB,

Int.

Rev.

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