FAB and FD mass spectrometry of transition metal complexes

International Journal of Mass Specfrometry and Ion Physics, Elsevier Scientific Publishing Company, Amsterdam -Printed

FAB AND

FD MASS

SPECTROMETRY

OF TRANSITION

499

46 (1983) 499-502 in The Netherlands

METAL

COMPLEXES

D. NEIBECKER,' D. FRAISSE,2 F. GOMEZ,3 and D.F. BAROFSKY3 I. TKATCHENKD,' -I 'Institut de Recherches sur la Catalyse du CNRS, 2, Avenue Albert Einstein, 69626 Villeurbanne Cedex (France). 2 Centre de_Spectrom&rie de Masse de Lyon, Service Centra'l d'Analyse du CNRS and Universite Claude Bernard, 6-P. 22-69390 Vernaison (France). 3 Department of Environmental Science, Oregon Graduate Center, 19600 N.W. Walker Road, Beaverton, Oregon 97006 (U.S.A.).

ABSTRACT FD and FAR mass spectra were obtained for the first time from a number of FD spectra are relacationic n3-allylic complexes of palladium and nickel. tively easy to obtain; they are characterized by an intense cation and very few FAB spectra have, to date, been difficult to produce; they are fragment ions. At precharacterized by a relatively small cation and numerous fragment ions. of sent FD is ,the method of choice for rapid, relatively easy characterization the molecular weight of the cation of these complexes. INTRODIJCTION Cationic efficient

Electron

l-3). tion

probe

cating (ref. been

n3-allylic catalysts

impact

leads

extensive

to information

characterization

only

study,

This

is believed

of this

important

application

nickel

vaporization

about

the

during

a number

of field

and

ligands

of cationic

of FAB to cationic

from

n3-allylic

complexes.

synthesized

by methods

indi-

complexes

mass

coordination

inser-

the probe

fast atom

as well

to be (ref.

complexes

from

reported

of compounds

shown

a direct

of these

(FD) and

to be the first

been

hydrocarbons

volatilization

desorption

class

have

of unsaturated

following

decomposition

by means

techniques.

ported

ionization

thermal

investigated

of palladium

the oligomerization

In the present

4).

(FAB)

complexes

for

have

bombardment spectrometric

as the first

re-

EXPERIMENTAL All where

samples (ref.

to either dendrite either

used

2,5,6).

bare

in this Samples,

tungsten

(8 JJFIW wire) a mixture

wire

were

dissolved (8 pm)

emitters

for

of DMF and glycerol

A Hitachi/Perkin-Elmer FD and

study

FAB experiments.

RMU-6E

0020-7381/83/0000-0000/$03.00

0

chloride,

or conventional

FD analysis.

Samples

(1:3) or in glycerol

single

The FD/FAB

in methylene

emitters

focusing

sample

probe

1983 Elsevier Scientific

reported were

else-

transferred

activated

were

carbon

dissolved

in

'alone for FAB analysis.

instrument is inserted

was used

for both

through

a vacuum

Publishing Company

500 lock assembly

at the back

square

of Cu/Be

serves

at the FAB

beam, used 2-3

sheet from

to produce

the

kV for

RESULTS

AND

Table principal TABLE FD and

both

metal

sample

generated

of the

FD and

I-+ II+

III

+.

an Ion Tech

The

spectra.

angle

keV,

across

15-20

PA

the end

primary

fie 'Id gun,

FABl 1NF saddle

ion source

a 2 mm

was

at a potential

was ,operated

of

DISCUSSION

1 lists

the coordination

features

of their

complex

FD and

FAB

salts

investigated

and

summarizes

the

spectra.

1, FAB mass

spectra

of cationic

n3-allylic

Methodb'c

Pd(PPh&+PFc-

FD: a.e.,

Pd(PCy&+PF;Pd(PBu3)2CPFG-

l3.5mA

FD: a-e., FD: a-e., b-w.,

11.5mA 10.5mA lO.OmA

FAB:

G

FAB:

DMF/G

FD: a-e., ll_OmA FD: a.e., ll-12mA b-w., 13.6mA FAB: DMF/G FD: a-e., b-w. FAB:

C <

6-7

with

FAB experiments_

IV---$ PdCP(OPh]alz+PFsV+ Pd(dppe) PF6-

VII

hotder

at an appropriate

A nondeflected,

gas with

Complexa

No.

A FD emitter

spot welded

support.

argon FAB

source.

Ni(PPHs)2+PFG-

8.2mA 14mA

DMF/G

FD: a-e., b-w.,

l2mA 14mA

FAB:G

complexes. m/zd(relative 685(H m(B 72l(H 581(M 581(H 201 (M 581(H 467(B 581(M 437(M 255(H 78l(B m(B 559(B 559(B m(H 425(H 187(B 425(H m(H 425(H 237(H 653(H 317(H 653(H 317(H 279(B 58(M)

abundancee)

423(M),

371(M),

: 565(B), , m(B),

393(M), 262(M) 281(B) 257(H), 437(M),

, I,

526(H),

510(h),

: 317(H), 335(H),

526(M) 510(M) 363(M): 307(M): 257(B): : 203(H), 201(H) 467(M), 310(M) 1 520-525(L), 503-506(L)

: %[;{

504(M),

were

obtained

for every

compound

427(H),

291(H),

315(M),

293(M),

357(~), 155(H), 370(H), 161(H), 582(L),

315(M), 101(H) 293(H) 101(B) 333(H),

: 213(H) 357(M),

: 101(H)

373(Mj,

: 187(B), 393(M),

: 194(H), 7

:

637(B), m(H)

: %j;j,

582(M),

: :;i[$,

115(H),

a* = n3-methallyl, = n3-crotyl, Ph = phenyl, Cy = cyclohexyl, bdppe = diphenyl phino l-2 ethane, tmtu = tetramethylthiourea. = activated carbon emitter, b-w. = bare wire emitter. DMF = dimethylformamide. ig;C_glycerol, c is underlined, masses given with lo6Pd and 58Ni. eB = base peak, H = >lO%, M = l-10%, L = ~1%. FD spectra

201(M) 257(H),

in Table

1.

Bu znbutyl,

At the best

anode

501 temperature mentation

the cation,

er emitter

in solution

or with

III leading

intense

and persists

until

peak

can

pear

in the spectra

FAB spectra present sample

The

sample

base

with

species

16 u above High-

mtL

as the major

reduced,

and

an

analogous

to the same

(two electron

donor).

either

the chelating

L, appears

only

re-

abundance

of less

is present

?n the spectrum is reached;

of the type

currents

greater

1 were

have yielded obtained

and

10%.

of III at 0 mA for ap-

to obtain.

spectra

At

under

milligram

then adding

I

10 mA.

mass

by dissolving

(DMF)

than

[(C,H,tmtu),PF,]+

difficult

sensible

of

no explanation

than

more

ligand,

in the spectra

of 6-10 mA Clusters

generally

with

234,

5).

Despite FD,

FAB spectra

of

pal fragmentation ion by losses at m/z

In contrast cribed

for

formation

135 are

attempts

FAB

amounts

this very

patterns

of the ally1

III

to VI,

FD resulting of this

III can also

of

concentrated

exhibits in an

be produced

is greater

than

produced

peak from

one and from

at m/z

facile

The

glycerol

ratio

alone.

fragmentation 257,

As with

is less

than

467 appear

of V (ref.

The

princi-

of the cat-

cluster

of

[PdSCNMe2]+.

pathway

des-

[C4H7PBu3]+.

by FD at OmA.

[(c+l6)+]/[c+]

alone at m/z

isotopic

to the species

peak at m/z

spe-

not be found

c+ peaks.

it is detected

glycerol The

437 and another

glycerol.

primary

base

could

to decomposition

ligand.

of VI corresponds the same

from

in its FAB spectra.

intense

m/t

[C4H70P(NMe2)s]+,

the synthesis

impurity

correspond

and one

around

monoisotopic

with

from

pallad-

291

clustered

principal

residual

moderately

intense

is's0

The

containing and m/z

peaks

respectively

it, this

in both cases radical

is evident FD mass

are

to detect

spectrum

fragment

of the mass

[HPd,]+.

which

fragments

([c-c~H~-c~H~]+,

consistent

III and VI exhibit

194 in the

427

distribution

[OP(NMe,),]+

specific

m/z

the structure

180 and

and

[HOP(NMe2)s]'. with

([Pd(dppe)]+), isotopic

213 is consistent at m/z

is c+ for V; the principal

peak

504 The

([PdPPh,l+).

of

peaks

frag-

complexes.

is formally

a relative

in Table

VII

and

were

little

to 15 U1 of glycerol.

ium are at m/z

peaks

437

current

in 5 U1 of dimethylformamide

mixture

cies

at m/z

of VI at heating

These

conditions.

with

at present.

V, VI,

mt.

L = Ligand

is not observed

of the compounds

III,

only

peak

be given

very

sensitive

is formed

Loss of one ligand,

a heating

this

metal, cation

4+bL++mtL

to [(q-allyl)PdL]+

A relatively

more

of the neutral

transition

and

III and VII exhibit

of

of these

in loss

case

7):

-

P(OPh),.

in every

peak

spectra

sulfonium

1 'L this fragmentation

Notably, dppe,

(ref.

‘L

t

The

or ally1

base

products

result

pathway.

phosphonium

action

and

to oxidation

temperatures

fragmentation

is the

The mass

is observed.

c+ corresponding

ally1

6,

The

Spectra

FD, oxidation

of III

from

DMF and glycerol

one.

The unexplained

in the FAB spectra

of III

502 FAB spectra

of a mixture

species,

change

ambiguity

The

containing

however,

not produce

279

any

(HOPPha+),

glycerol

exhibit

observed

the adduct,

[PdG]+

in the mass decomposition

165, and

115.

solubil ities

FAB spectra.

spectra

(G=glycerol)

range

of the palladium is not seen.

corresponding

of this complex

In addition,

ex-

161 is detectable

not in the other in the FAB

ligand

product,

of the relative

[methallyl- Pd]+ at m/z but

the

its fragmentation

indication

spectra

ions

extensive

In glycerol,

ions at m/z

fragment

mixture

in and

(tmtu)l+,

is generally

ion, Pd+,

complexes;

FAB does of VII.

in the

and VI

as g ive an

as well

of the two complexes.

The metal

III

[(C,H,)Pd(PBus)

[Pd(PBu,)(tmtu)]+, without

of

to the cation

occurs

Ni+ and

yielding

[NiG]+

are

ob-

served. CONCLllSIOl\I FD mass relatively

spectra easy

very

few fragment

cult

to produce

and

Liquid

selection

is not well

is the method molecular

suited

of choice

weight

must

complexes

By contrast cation

be further

to these

for a rapid,

of the cation

FAB spectra

in this

small

have

study yielded peak

and

sensitive

comparatively

spectra)

complexes.

are

peak and

been diffiand are

fragment

glycerol's

facile

and nickel

cation

to date

numerous

investigated;

highly

of these

of palladium

by an intense

characterized

(not all compounds

by a relatively

ability

are

ion peaks.

characterized matrix

n3 -allylid

of cationic

to obtain

ion peaks.

protonating At present

determination

FD

of the

complexes.

REFERENCES 1 2 3 4

5 6 7

C.A. Tolman, J. Am. Chem. Sot., 92 (1970) 6777-6784. R.B.A. Pardy and I. Tkatchenko, J.C.S. Chem. Comm., (1981) 49-W. P. Grenouillet, 0. Neibecker, J. Poirier, and I. Tkatchenko, submitted for publication in Angew, Chem., Engl. Ed. (1982). F. Gomez and II, Fraisse, Centre de SpectromGtric de Masse de Lyon, Service Central d’Analyse du CNRS and Universite Claude Bernard, Vernaison, France, unpublished data (1981). P. Grenouillet, D. Neibecker,' and I. Tkatchenko, Inorg. Chem., 19 (1980) 3189-3191. D. Neibecker and B. Castro, Inorg. Chem., 19 (1980) 3725-3729. D. Neibecker and B. Castro, J. Organomet. Chem. 134 (1977) 105-113.

This work was supported 5RDl AMZ0937-05).

by the

CNRS

(France)

and by the

NIH

(USA)

(Grant

No.