Aryl complexes of platinum(I1).

A study of the bonding between platinum and

tertiary phosphine, arsine, and stibine
A. D. WESTLAND
AND M. NORTHCOTT
Departtnetzt of Clzetnistry, Utziversity of Otta~va,Ottawa, Canada
Received March 25, 1970

Phenyl and fluorophenyl complexes but not alkyl complexes of platinum may be prepared from
(Et3Sb),PtClz by Grignard reactions. Dipole moment and 19F nuclear magnetic resonance studies
indicate a slight gradation in electronic properties which correlates with previous equilibrium studies.
Can. J. Chem. Downloaded from cdnsciencepub.com by 49.36.104.29 on 12/17/23

Canadian Journal of Chemistry, 48,2907 (1970)

Despite the existence of numerous complexes
of platinum group metals containing tertiary
phosphines, arsines, and stibines, little informa-
tion is available as yet concerning the relative
bond characters of the metal-ligand coordinate
links. Previous work in this laboratory on equi-
libria involving the formation of five-coordinate
complexes of platinum and palladium has sug-
gested that the positive charge on the metal atom
increases in the order of ligands: phosphine -+
arsine -+ stibine (1, 2). The argument presented
which was based on variations in d,d, bonding
is at variance with the ideas of previous workers
who believed that phosphorus encourages the
strongest component of n-bonding amongst the
Group V donor atoms (3). More recently,
Venanzi has argued that d,-d, bonding has been
much overemphasized and that most data may
equally well be interpreted by a proper recog-
nition of a-inductive effects (4).
Parshall has developed a technique based upon
an examination of the 19F nuclear magnetic
resonance (n.m.r.) chemical shift in meta and
para positions of a phenyl group bonded to a
platinum atom (5). This group is placed in a
coordination position trans to the ligand whose
n-bonding potential is being investigated. Bruce
has examined 19Fresonance in pentafluorophenyl
complexes (6). However, Church and Mays have
questioned Parshall's conclusions concerning n-
bonding, for when they applied the 19F n.m.r.
technique to a series of cationic platinum com-
plexes, the results seemed to indicate that a a-
inductive mechanism was more strongly oper-
ative than a n mechanism (7).
The present state of confusion about interpret-
ing the more indirect physical phenomena in
chemical terms suggests that further work is
much needed. The present paper examines the
comparison of dipole moment data and 19F
resonance spectra obtained for complexes of the
type c~s-(E~,M),P~(C,H,F)~ where M = P, As,
or Sb.
Experimental
Reagents
The compounds PtL2C12where L = Et,P, Et3As, and
Et3Sb were prepared by established procedures (8) from
commercial grade platinum sponge. The ligands were
prepared in the manner described by Adams and Raynor
(9). Bromofluorobenzenes supplied by Aldrich Chemical
Company were distilled prior to use. Grignard reagents
were prepared in diethylether which had been freshly dis-
tilled from a n ethyl Grignard solution containing excess
magnesium.
Preparatiot~of Aryl Complexes
The cis-diary1 complexes were prepared by a method
of which the following is a typical example.
cis-(Et,Sb) 2PtPIi2
Solid cis-(Et,Sb),PtC12 (I g) was added slowly to a
cooled (-60 "C) solution of phenylmagnesium bromide
in ether (50cc). After the addition was complete, the
sample was allowed t o warm to room temperature a t
which point it was stirred for 1 h. The solution was then
cooled to 0 "C and hydrolyzed with water (50 cc).' The
ether layer was dried over MgS04 and the solvent re-
moved by evaporation. The residue was placed o n a 100 g
alumina column and eluted with a 5 % solution of diethyl-
ether in light petroleum. A pure fraction was located by
thin layer chromatography (t.1.c.) and this solution was
evaporated t o dryness. The product, which consisted of
white needles, was recrystallized from methanol in 29%
yield.
cis atld trans- (Et, As) 2Pt(m-FC6 H4)
c i s - ( E ~ , A S ) ~ P ~(0.5
C ~ ,g) was added t o m-FC6H4MgBr
(1.16 g) in ether (50 cc) which had been cooled to - 60 "C.
The solution was allowed t o warm to room temperature
and it was stirred for 2 h. After hydrolysis with NH,Cl
solution, the dried ether layer was evaporated t o an oil
which was purified chromatographically on an alumina
column. Elution with petroleum ether (30-60") gave white
tratz~-(Et,As),Pt(m-FC~H~)~ which was recrystallized
from methanol. Further elution with 5 % ether - petro-
'Dilute HCl acid was used t o prepare the complexes
containing triethylphosphine or triethylarsine.
 2908 CANADIAN JOURNAL O F CHEMISTRY. VOL. 48, 1970

TABLE 1
Analytical data for aryl complexes of platinum(I1)

Melting Anal. Calcd. (%) Anal. Found (%)

point
Compound ("C) Yield C H F C H F
C ~ S - [ ( C ~ H ~ ) ~ P ] ~ P ~ ( ~ 159-160
- F C ~ H ~ )47~ 46.38 6.16 6.11 46.23 6.22 5.96
~~~-[(CZH~)~PIZP~(P-FC~H~)~ 158-159 38 46.38 6.16 6.11 46.54 6.14 6.02
~ ~ S - [ ( C Z H ~ ) ~ A ~ ] ~ P ~ 123-124
( ~ - F C ~ 40H~)~40.63 5.40 5.36 40.56 5.51 5.41
trans-[(C2H5)3As12Pt(m-FC6H4)2 144-145 13 40.63 5.40 5.36 40.47 5.39 5.47
~ ~ S - [ ( C Z H ~ ) ~ A ~ I ~ P ~ ( P125-126
- F C ~ H ~ )38~ 40.63 5.40 5.36 40.64 5.49 5.28
~~S-[(C~H~)~S~]~P~(~-FC~H,), 78-79 22 35.89 4.77 4.73 35.75 4.89 3.44
~ ~ S - [ ( C Z H ~ ) ~ S ~ I ~ P ~ ( P -92-93
F C ~ H ~ )35~ 35.89
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4.77 4.73 35.21 4.71 4.66

trans-[(CzH5)3Sb]ZPtCl(p-FC6H4) 106-107 28 29.08 4.61 2.55 28.66 4.60 2.23
cis- [(CzH5)3SblzPt(C6H5)z 68-69 29 37.57 5.25 37.50 5.52
[(CsHs)3PlAu(m-FC6H4) 146-147 64 52.04 3.45 3.42 52.19 3.43 3.33
(dec.)

leum ether gave white ci~-(Et~As)~Pt(m-FC6H~)2 which which employs Grignard reactions (12). Although
was recrystallized from methanol. we were successful in making aryl complexes,
trans- (Et3Sb) ~ P t c / ( p - F c ~ H ~ ) cis-dichlorobis-(triethylstibine)platinum(II) gave
A solution of cis-(Et3Sb),PtClZ which had been treated
with p-FC6H4MgBr as described above, was hydrolyzed dark decomposition products when it was added
with 4 N HCI. A t.1.c. of this solution gave a spot with an to strongly cooled ethylmagnesium bromide. We
Rf value of about one half that for (Et3Sb)zPt(p-FC6H4)2. conclude that alkyl compounds of this type are
Purification by chromatography using 10% ether - petro- too unstable to be prepared by the Grignard
leum ether gave white tran~-(Et~Sb)~PtCl(p-FCJl~) method and that tertiary stibine is less effective
which was recrystallized from methanol.
Prolonged treatment with HCl solution resulted in than tertiary arsine or phosphine in stabilizing
complete conversion back to (Et3Sb),PtClz. Hydrolysis organometallic derivatives of platinum. The
with NH4CI solution also resulted in replacement of one meta-fluorophenyl complex containing Ph3Sb
of the aryl groups of the diary1 complex although not so was least stable of the platinum complexes and it
rapidly as when HCl was used.
decomposed readily during evaporations and
Nuclear Magnetic Resonance Spectra chromatographic treatment. The para-fluoro-
Proton n.m.r. spectra were obtained with a Varian phenyl complex was more stable owing possibly
Associates model T-60 spectrometer. Fluorine spectra to an enhancement of the n-bonding from
were obtained with a Varian Associates model HR-100
spectromerer using side-band modulation for calibration. platinum to carbon.
Spectra were run using chloroform or deuterochloroforn~ Still less stable was (Ph3P)Au(m-C,H,F). Re-
as a solvent and with external reference substances. peated attempts to prepare the para-fluorophenyl
Dipole Moments analogue failed as the solutions were found to be
A Wissenschaftlich-Technische Werkstatten Dipol- so unstable at room temperature, they could not
meter model DM-01 was employed for dielectric constant be worked up. In striking contrast to our ex-
determination at 25 "C. Samples were dissolved in perience, Vaughan succeeded in preparing this
benzene.
Smith's method was used for evaluating the dipole
compound in a Grignard reaction which involved
moment values (10). The results were consequently refluxing at 60" (13). It may be that the quality of
corrected for electronic polarization but not atomic the reagents is of crucial significance here.
polarization. Melting points and analyses of the compounds
Analyses prepared are given in Table 1.
Analyses were performed by the firm of A. Bernhardt The location of the fluoro group in the phenyl
Mikroanalytisches Laboratorium, Elbach, West Ger- rings was verified in all cases by proton magnetic
many. resonance spectra. The stereochemistry of the
Results and Discussion isomers was established by dipole moment
At the commencement of our work no organo- measurements. The data associated with these
metallic compounds of platinum stabilized by a measurements is presented in Table 2. Refractive
tertiary stibine had been reported. Recently, how- indices were measured for one isomer in each
ever, triphenylstibine complexes wcre described case. Solutions of the other isomer were assumed
by Kistner et al. (11). These were made by a to have the same molar refractive index.
method which differed fundamentally from that As expected, the para-fluorophenyl isomers
 WESTLAND AND NORTHCOTT: ARYL COMPLEXES

TABLE 2
Dipole moment measurements on aryl complexes of platinum(I1)
--
Weight
fraction,
(X 104) AEIW A(~~)I,v &)
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trans- [(CzH,)3Sb],PtCl(p-FC,H,) 13.533

271.6

have a somewhat higher dipole moment in each solvation effects are responsible or that indeed,
case than the meta-fluorophenyl analogues. The as previously suggested (1, 2), the n electron drift
trend in moment exhibited by the phosphorus, from platinum to antimony is greater than that
arsenic, and antimony analogues is interesting al- toward either arsenic or phosphorus. In any case,
though one must be careful not to place too much the dipole moment data appear to reflect the
reliance upon any given interpretation. We have same influences as do the equilibrium data of our
obtained for both (Et,P),PtPh, and (Et,As),- previous studies.
PtPh, dipole moment values of 7.2 D. These agree When interpreted in the manner proposed by
well with the values obtained by Chatt and Shaw Parshall (9, the 19F n.m.r. spectra indicate a
(12). The value obtained for (Et,Sb),PtPh, was marginally greater n-bonding ability on the part
6.3 D. The generally lower value for the antimony of triethylstibine relative to triethylphosphine.
analogue is observed in the chloro compounds The last column in Table 3 labelled "n-bonding
(Et,M),PtCl, (13) and the meta- and para-fluoro- index" contains the differences between values in
phenyl series of compounds as well. One might the preceding two columns. These differences,
assume that the Sb-Pt-Sb bond angle is larger according to Parshall's argument, are a measure
than the As-Pt-As and P-Pt-P angles which of the extent to which the aromatic ring draws
would have the effect of diminishing the observed electron density from the platinum atom by a
resultant of the bond moments. Molecular models mesomeric mechanism. This should bear an in-
fail to indicate categorically whether steric verse relationship to the degree of n-bonding
crowding must occur. However, we have pre- to the ligand in the trans position.
viously shown a similar trend in the moments of Parshall observed only a small variation in the
the compounds (Ph,M)AuBr where the steric n-bonding index as do we. This represents an
factor does not arise (2). It is conceivable that uncertain result. Furthermore, Dewar has pointed
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 48, 1970

TABLE 3
The 19Fchemical shift data for fluorophenyl derivatives of platinurn(I1) and gold(1)

Chemical shift* (p.p.rn.)

n-Bonding
Compound rneta-Fluoro para-Fluoro index (p.p.rn.)

*Relative to fluorobenzene.Values are rounded off to the nearest 0.05 p.p.m.

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out that the influence of remote groups on 19F (Ph3P)AuC6H5(6.2 D) is large relative to 5.1 D
n.m.r. chemical shifts is a vector quantity while estimated for the linear (Et3P)PtC6Hj grouping2
chemical equilibria and reactivity depend upon a (18). Vaughan has commented on the low degree
scalar quantity (14). Since the exact geometry of of electron delocalization onto the phenyl ring in
these molecules is not known and hence the (Ph,P)Au(p-FC6H,) as estimated using Parshall's
orientation of the meta C-F bond may differ technique. Further work on gold(1) is being
somewhat from one compound to another, it may hampered by the generally low stability of its
be that the "n-bonding index" is a more complex complexes.
quantity than Parshall or Church and Mays (7)
suggested. This work was supported by a grant from the National
The chemical shift of the para fluorine atom Research Council of Canada.
alone may be a simpler quantity for the orienta-
tion if the para C-F bond is fixed. Indeed, l . A. D. WESTLAND.J. Chern. SOC. 3060 (1965).
Hogben et al. (15) concluded that it is determined 2. A. D. WESTLAND.Can. J. Chern. 47,4135 (1969).
3. J. CHATT,L. A. DUNCANSON, B. L. SHAW,and L. M.
largely by o ~ ,the Hammett-Taft VENANZI. Discuss. Faraday Soc. 26, 131 (1958).
parameter (16), and so to a first approximation 4. A. PIDCOCK,R. E. RICHARDS,and L. M. VENANZI.
it is a measure of n: interaction between the phenyl P r ~ c Chern.
. Sot. 184 (1962).
5. G. W. PARSHALL.J. Arner. Chern. Soc. 88, 704
ring and its substituent. The series of values for (1966).
the para fluorine chemical shift given in Table 3 6. M. I. BRUCE. J. Chern. Soc. (A), 1459 (1968).
agree qualitatively with the trend in dipole 7. M. J. CHURCH
3074 (1968).
and M. J. MAYS. J. Chem. Sot. (A),
rmments. The same trend was observed in the 8. GMELIN'S Handbuch der anorganischen Chernie.
chemical shift for the para hydrogen atoms in the Platin. Teil D, System Nurnrner 68. Verlag ~ h e r n i e ,
pyridine trans-(Pr3M)PtC12~~, 1957.
9. D. M, ADAMSand J, B. RAYNOR.Advanced prac-
though in these the "n-bonding index" difference tical inorganic chemistry. Wiley, 1965. p. 117.
values did not correlate with any obvious 10. J. W. SMITH. Trans. Faraday Soc. 46, 394 (1950).
ical facts (17). While we cannot account for these 11. C. R. KISTNER, J. D. BLACKMAN,
Inorg. Chern. 8, 2165 (1969).
and W. C. HARRIS.
various observations with any certainty, we 12. J. CHATTand B. L. SHAW. J. Chern. Soc. 4020
suggest that their (1959)
may be significant' 13. J. CHin and R. G. WILKINS. J. Chern. Sot. 4300
In tran~-(Et,As),Pt(nz-FC~H~)~ the chemical (1952).
shift of the meta fluorine atom is slightly higher 14. M. J. S. DEWARand T. G. SQUIRES.J. Amer. Chern.
Soc. 90,210 (1968). W. ADCOCK and M. J. S. DEWAR.
than that of the cis isomer. The value is similar J. Amere Chern. Sot. g9, 379 (1967).
to that reported for tr~ns-(Et,P),Pt(rn-FC~H~)~ 15. M. G. HOGBEN, R. G. GAY,and W. A. G. GRAHAM.
(5). We have also included in Table 3 the 19F J. Arner. Chern. Soc. 88, 3457 (1966).
16. R. W. TAFTand J. W. RAKSHYS, JR. J. Amer. Chern.
shift for (Ph3P)Au(m-FC6H4) which is So,. 87, 4387 (1965) and references cited therein.
seen to be lower than comparable values for the 17. J. CHATTand A. D . WESTLAND.J. Chern. Soc. (A),
platinum Vaughan obtained a higher 18. G. 88 (1968).
CALVIN, G. E. COATEs,and P. S. D I ~ O N .Chem.
value for this compound but he worked in a ~ n d 1628
. (1959).
different solvent (13). Although this low value for
the chemical shift in the gold compound would
ZThisis I / J2 (1,) where PI,is the observed moment for
seem to indicate that there is less electronic charge cis-(Et3P)zPt(C6H5)z (7). The negative end of the dipole
build-up in the phenyl ring, the dipole moment of lies between the phenyl rings.