344 Organometallics 1986,5, 344-348

A Platinum Cluster Complex Containing a Triply Bridging

Carbonyl: The Synthesis and Structure of
(p,-Carbonyl)tris[ p-bis( diphenylphosphino)methanel- friangulo -
t riplatinum(2 ) Hexafluorophosphate+
George Ferguson," la Brian R . Lloyd,lb and Richard J. Puddephatt'lb
Departments of Chemistry, University of Guelph, Guelph, Ontario, Canada N l G 2W1, and University of Western
Ontario, London, Ontario, Canada N6A 587

Received June 24, 1985

Reaction of [Pt(02CCFd2(dppm)], dppm = Ph2PCH2PPh,with CO in aqueous methanol gives the cluster

complex [Pt3(p3-CO)(p-dppm)3][CF3C02]2 (1) which may be converted to the [PF6]-salt 2. The complexes
1 and 2 are the first complexes reported to contain the Pt3(p3-CO)group and are significant as models
for CO chemisorbed at a threefold site on a Pt surface. Complexes 1 and 2 were characterized by elemental
analysis, IR, and lH, 31P,and '%PtNMR and by X-ray crystallography (for 2, as the acetone solvate). Crystals
of 2.C3H60 are triclinic, space group PI, with 2 = 2, a = 14.090 (2) A, b = 22.711 (4) A, c = 13.637 (4) A,
cy = 103.43", = 99.52 (2)", and y = 106.72 (1)".The structure was solved by the heavy-atom method
and refiied by full-matrix least-squares calculations with anisotropic thermal parameters for the non-phenyl
and non-solvate atoms. At convergence,R = 0.035 for 6234 reflections with I > 3a(I). The crystal structure
contains discrete cations, anions, and acetone solvate molecules. The Pt atoms of the cation form a triangle
with Pt-Pt = 2.613-2.650 (1)A. The carbonyl ligand occupies a triply bridging site with Pt-C = 2.080-2.095
(9) A. The atoms of the Pt3P6 moiety are only approximately coplanar; the Pt-P distances are in the range
2.262-2.304 (2) A. The three PtzPzCfive-membered rings adopt envelope conformations with the CH2
moiety at the flap.

Introduction and it was readily converted to [Pt3(p3-C0)(p-dppm),]-

When carbon monoxide is adsorbed onto a Pt(ll1)
surface, the on-top (terminal) sites are occupied first [v-
(CO) = 2110 cm-'1 but at higher coverage the twofold ( p 2 )
sites are preferred [v(CO) = 1840-1875 ~ m - ' ] . ~Recently
it has been shown that threefold (p,) sites are also occupied
a t high coverage [v(CO) = ca. 1810 cm-lI2 and that the
energy difference between the pz-CO and p,-CO groups is
only 4 ( f l ) kJ mol-'. From the analogy between surfaces
and clusters,, it should therefore be possible to prepare
cluster complexes containing Pt3(p3-CO)units. However,
even high nuclearity clusters such as [Pt19(CO)zz]4-or
[Pt30(CO),]2- contain only terminal and p2-C0
We now report the first synthesis of a complex containing
the Pt3(p3-CO)group and its characterization by spectro-
scopic techniques and by X-ray crystallography as [Pt3-
( c L ~ - C O ) ( P - ~ P[PF,IY(CH,)ZCO,
P~)~I dppm =
Ph2PCH2PPh2.6
Results and Discussion
Reaction of [Pt(O&CF,),(dppm)] with carbon monoxide
a t 100 "C for 3 days in methanol-water solvent gave the
complex [Pt&.~~-CO)(p-dppm),] [CF3COzI2(1) in 97 % yield.
This complex was formed in spectroscopically pure form,
(1) (a) University of Guelph. (b) University of Western Ontario.
(2) Baro, A. M.; Ibach, H. Surf. Sci. 1981, 103, 248. Hayden, B. E.;
Bradshaw, A. M. S u r f . Sci. 1983, 125, 787.
(3) Muetterties, E.L.; Rhodin, T. N.; Band, E.; Brucker, C. F.; Pretzer,
W.R. Chem. Rev. 1979, 79,91.
(4)Clark, H. C.; Jain, V. K. Coord. Chem. Rev. 1984, 55, 151.
( 5 ) Semitriply bridging carbonyls are observed in some heteronuclear
clusters. Bender, R.; Braunstein, P.; Dusausoy, Y.; Protas, J. J. Orga-
nomet. Chem. 1979, 172, C51. Bender, R.; Braunstein, P.; Jud, J. M.;
Dusausoy, Y.Inorg. Chem. 1984, 23, 4489.
(6) The synthesis of a related palladium complex, [Pd3(p3-CO)(p-
dppm)3][CF3C0,],, has been reported recently. ManojloviE-Muir, Lj.;
Muir, K. W.; Lloyd, B. R.; Puddephatt, R. J. J. Chem. SOC.,Chem.
Commun. 1983,1336. Lloyd, B. R.; Puddephatt, R. J. Inorg. Chim.Acta
1984, 90, L77. ManojloviE-Muir, Lj.; Muir, K. W.; Lloyd, B. R.; Pudde-
phatt, R. J. J. Chem. SOC.,Chem. Commun. 1985, 536.
[PF612(2) by reaction in methanol with excess NH4[PF6].
Complex 2 was characterized crystallographically as its
acetone solvate.
Description of the Structure of 2.(CH3)&0. The
structure contains discrete cations, anions and loosely
entrapped acetone of solvation separated by normal dis-
tances. In the cation (Figure 1)the Pt atoms form a tri-
angle with Pt-Pt distances 2.613 (l), 2.638 (l), and 2.650
(1)A and Pt-Pt-Pt angles 59.23 (11, 60.17 (l), and 60.60
(1)"(see Table I). The carbonyl ligand occupies a triply
bridging site, with Pt-C distances 2.080 (9), 2.089 (E!), and
2.095 (9) 8, and Pt-C-Pt angles 77.6-78.8(3)". The Pt3P6
atoms are only approximately coplanar (the deviation of
the P atoms from the P&plane are as follows: P11,-0.276
(2); P12, -0.013 (2); P21, -0.619 (2); P22, 0.154 (2); P31,
-0.495 (2); P32, -0.069 (2) A). The Pt-P distances are in
the range 2.262 (2) to 2.304 (2) A with a mean value of
2.282 A. All three Pt2P2Crings adopt envelope confor-
mations with the methylene carbon a t the flap; two of the
atoms, C(2) and C(3), are folded toward the bridging
carbonyl and the other, C(4), is folded away. Presumably
these conformational variations improve the packing of the
ions. In the related palladium complex [Pd,(p,-CO) ( p -
dppm),] [CF3CO2I2,the corresponding Pd-Pd, Pd-C, and
Pd-P distances are 2.576 (1)-2.610 (2) A, 2.09 (1)-2.18 (l),
and 2.296 (3)-2.340 (3) A, respectively.6 The structures
are very similar, but, in the platinum complex, the met-
al-metal distances are slightly longer and the metal-
phosphorus and metal-carbon distances are slightly shorter
than in the palladium complex. The Pt-Pt distances in
2 are slightly shorter than the range of Pt-Pt distances of
2.672 (2)-2.790(7) A found in platinum clusters such as
Y ~ )=~ CI Y C ~ O -
[ P ~ , ( ~ ~ L - S O Z ) ~ [( PP~P~~(~P)-~CIO, ) ~ ( P C(CY
hexyl), and [Pt4(p-CO)a(PMe2Ph)4]7-'o but lie in the range
(7) Moody, D. C.; Ryan, R. R. Inorg. Chem. 1977,16, 1052.
(8)Albinati, A,; Carturan, G.; Musco, A. Inorg. Chim. Acta 1976,16,
L3.

0216-7333/S6/2305-0344$01.50/0 0 1986 American Chemical Society

A Platinum Complex Containing a Triply Bridging Carbonyl
Figure 1. A view of the [Pt3(~-CO)(pdppm)3]2+ cation with the
crystallographic numbering scheme. For clarity only the phenyl
carbon bonded to each phosphorus atom is shown (phenyl ring
atoms are numbered Cnl-Cn6 where n = 1-12).
of Pt-Pt bond lengths of 2.584 (2)-2.769 (1)A found for
diplatinum(1) complexes."J2 These observations are
consistent with the formal oxidation state for platinum of
+ 2 / 3 for complex 2 and with the presence of Pt-Pt single
bonds in the cluster.
Spectroscopic Properties of 1 and 2. The carbonyl
stretching frequencies of 1 and 2 were a t 1750 and 1765
cm-', respectively, which may be compared to the value
of v(C0) of 1810 cm-' for CO at a threefold site on Pt(ll1).
It seems that back-bonding from platinum into a* orbitals
of CO is reasonably strong despite the 2+ charge on the
cluster. The v(C0) values for 1 and 2 were -70 cm-I to
lower energy than those of the analogous palladium com-
plexes; similar differences have been observed in other
carbonyl complexes such as [M,Cl,(p-CO)(p-dppm),], M
= Pd or Pt.13J4
The 1H(31PJNMR spectra of 1 and 2 each contained an
AB quartet for the CHAHBP,protons showing that there
is no plane of symmetry containing the Pt3P6C3 atoms of
the Pt,(dppm), unit. This nonequivalence of the CH2P2
protons arises due to the presence of the p3-CO ligand on
one side of the Pt3 triangle.
The 31P(1HJNMR spectra of 1 and 2 each contained a
singlet with very complex and incompletely resolved sat-
ellites due to coupling to lg6Pt,as shown in Figure 2a. The
complexity arises in part from the superposition of reso-
nances due to the Pt,P6 systems containing 0 (29% natural
abundance), 1 (44%), 2 (23%), and 3 (4%) lg6Ptatoms.
The spectra were insufficiently resolved to allow a full
simulation, but the coupling constant lJ(PtP) was easily
obtained and partial simulation of the system containing
one lg5Ptcenter showed that there is one large ,J(PP)
coupling of 170 Hz in 1 and 140 Hz in 2 [illustrated by i
in Figure 21. This large coupling is tentatively assigned
as that between the nearly trans phosphorus atoms P-
(ll)P(22), P(21)P(32),and P(12)P(31),defined in Figure
1. The long-range couplings V(PtP) were too small to be
resolved.
In the 195Pt('HJNMR spectrum (Figure 2b) the most
prominent feature is the triplet arising from the isotopomer
containing a single lg5Ptatom, due to coupling to the two
(9) Chatt, J.; Chini, P.; Dahl, L. F.; Vranka, R. G. J. Am. Chem. SOC.
1969.I -91.
_._. 1574.
- , - - - - -
(IO) Braunstein, P.; Jud, J.-M.; Dusausoy, Y.; Fischer, J., Organo-
metallics 1983, 2, 1980.
(11) ManojloviE-Muir, Lj.; Muir, K. W.; Solomun, T. J. Organomet.
Chem. 1979,179,479.
(12) ManoiloviE-Muir. Li.: Muir, K. W. J. Organomet. Chem. 1981.
219, 129.
(13) Balch, A. L.; Benner, L. S. J. Am. Chem. SOC.1979, 100, 6099.
(14) Brown, M. P.; Puddephatt, R. J.; Rashidi, M.; Seddon, K. R. J.
Chem. Soc., Dalton Trans. 1978, 1540.
Organometallics, Vol. 5, No. 2, 1986 345
-2800 -2900 -3000 6/ppm
10 0 - 10 -20 6/ppm
Figure 2. NMR spectra of complex 2: (a) NMR spectrum
(121.4MHz). The inset shows the lg5Ptsatellites at higher sen-
sitivity and (i) shows the large J(PP) coupling (see the text). (b)
lg5PtNMR spectrum (64.3MHz).
directly bound phosphorus atoms. Satellite spectra, arising
from the isotopomer with two lg6Ptatoms, were also ob-
served (Figure 2b) and allowed the coupling constant ' J -
(PtPt) = 540 Hz to be determined. The value is compa-
rable to values found in other triangular Pt, ~ l u s t e r s . ' ~ J ~
Another feature of interest is the significant difference
in the 31Pand lg6Ptchemical shifts between complexes 1
and 2. A similar effect has been observed in the analogous
palladium complexes,6 and it is rationalized by assuming
that in 1 a trifluoroacetate ion is weakly coordinated to
platinum a t the triply bridging site, which is vacant in
complex 2. Complex 1 may therefore be better charac-
terized as [Pt3(02CCF3)(p3-CO)(p-dppm)3] [CF,CO,].
The spectroscopic data are clearly consistent with the
structure of 2 being the same in solution as in the solid-
state structure determined crystallographically (Figure 1).
Bonding in Complex 2. The bonding in complex cation
2 can be treated in several ways. First, it can be seen that
each platinum atom is in oxidation state + 2 / 3 and that,
if the Pt-Pt bonds within the Pt3triangle are single two-
electron bonds, each platinum atom has a 16-electron-va-
lence shell. Secondly, the total number of valence electrons
in the cluster is 42 and polyhedral skeletal electron pair
theory predicts a "latitudinal" structure with a planar PbP6
ske1et0n.l~ The theoretical work is based on a neutral
Pt&6 cluster but, since the carbonyl ligand in 2 provides
two electrons to make up for the 2+ charge on the cluster
cation, the result is the same. In a latitudinal [Pt&]'+
cluster the LUMO is expected to be an orbital of Al yym-
metry derived from a linear combination of the hybrid 6s
5d,2 orbitals directed toward the center of the Pt3trian-
gle.17 If the CO ligand donates two electrons into this Al
molecular orbital, it would be expected to occupy the
symmetrical triply bridging coordination site as observed.
It is possible, and only detailed MO calculations could
(15) Moor, A.; Pregosin, P. S.; Venanzi, L. M. Znorg. Chim.Acta 1981,
48, 153.
(16) Moor, A.;Pregosin, P. S.; Venanzi, L. M. Znorg. Chim.Acta 1981,
48,153.
(17) Evans, D. G.; Mingos, D. M. P. J. Organomet. Chem. 1982,240,
321. The planarity of the Pt8L, skeleton is most simply rationalizing in
terms of the isolobal analogy of PtLl and CH:, fragments, so that planar
PtSL6 is isolobal with cyclopropane. Hoffmann, R. Angew. Chem., I n t .
Ed. Engl. 1982, 21, 711.
346 Organometallics, Vol. 5, No. 2, 1986 Ferguson et al.

Table I. Selected Interatomic Distances and Angles

a. Bond Distances (A)
atom 1 atom 2 dist atom 1 atom 2 dist
Ptl Pt2 2.638 (1) P12 C31 1.807 (8)
Ptl Pt3 2.650 (1) P12 C41 1.807 (8)
Ptl P11 2.304 (2) P21 c2 1.848 (8)
Ptl P1.2 2.284 (2) P21 C51 1.804 (8)
Ptl c1 2.095 (9) P21 C61 1.813 (8)
Pt2 Pt3 2.613 (1) P22 c3 1.858 (8)
Pt2 P21 2.277 (2) P22 C71 1.789 (8)
Pt2 P22 2.271 (2) P22 C81 1.792 (8)
Pt2 c1 2.089 (8) P31 c3 1.823 (8)
Pt3 P31 2.294 (2) P31 c91 1.814 (8)
Pt3 P32 2.262 (2) P31 ClOl 1.817 (8)
Pt3 c1 2.080 (9) P32 c4 1.832 (8)
P11 c4 1.843 (8) P32 Clll 1.803 (8)
P11 c11 1.807 (8) P32 c121 1.812 (8)
P11 c21 1.811 (8) 01 c1 1.154 (9)
P12 c2 1.835 (8)
mean P-F = 1.570 (7) A; mean aromatic C-C = 1.38 (1)A
b. Bond Angles (deg)
atom 1 atom 2 atom 3 angle atom 1 atom 2 atom 3 angle
Pt2 Ptl Pt3 59.23 (1) Pt2 Pt3 c1 51.3 (2)
Pt2 Ptl P11 154.10 (5) P31 Pt3 P32 113.28'(8)
Pt2 Ptl P12 94.86 (5) P31 Pt3 c1 121.4 (2)
Pt2 Ptl c1 50.8 (2) P32 Pt3 c1 115.3 (2)
Pt3 Ptl P11 95.69 (5) Ptl P11 c4 109.5 (3)
Pt3 Ptl P12 154.09 (6) Ptl P11 c11 119.3 (3)
Pt3 Ptl c1 50.4 (2) Ptl P11 c21 113.1 (3)
P11 Ptl P12 109.98 (8) c4 P11 c11 103.6 (4)
P11 Ptl c1 119.8 (2) c4 P11 c21 105.9 (4)
P12 Ptl c1 115.0 (2) c11 P11 c21 104.4 (4)
Ptl Pt2 Pt3 60.60 (1) Ptl P12 c2 111.6 (3)
Ptl Pt2 P21 92.62 (5) Ptl P12 C31 121.1 (3)
Ptl Pt2 P22 157.63 (5) Ptl P12 C41 108.7 (3)
Ptl Pt2 c1 51.0 (2) c2 P12 C31 103.6 (4)
Pt3 Pt2 P21 149.30 (6) c2 P12 C41 105.1 (4)
Pt3 Pt2 P22 97.34 (5) C31 P12 C41 105.6 (4)
Pt3 Pt2 c1 51.0 (2) Pt2 P21 c2 107.6 (3)
P21 Pt2 P22 109.64 (8) Pt2 P21 C51 119.8 (3)
P21 Pt2 c1 124.6 (2) Pt2 P21 C61 111.1 (3)
P22 Pt2 c1 113.4 (2) c2 P21 C51 105.2 (4)
Ptl Pt3 Pt2 60.17 (1) c2 P21 C61 106.0 (4)
Ptl Pt3 P31 148.86 (5) C51 P21 C61 106.2 (4)
Ptl Pt3 P32 94.46 (5) Pt2 P22 c3 109.4 (3)
Ptl Pt3 c1 50.9 (2) Pt2 P22 C71 109.1 (3)
Pt2 Pt3 P31 91.04 (5) Pt2 P22 C81 120.9 (3)
Pt2 Pt3 P32 154.58 (5) c3 P22 C71 104.51 (4)
c3 P22 C81 105.4 (4) c4 P32 c121 106.9 (4)
C71 P22 C81 106.3 (4) Clll P32 c121 106.2 (4)
Pt3 P31 c3 108.1 (3) Ptl c1 Pt2 78.2 (3)
Pt3 P31 c91 114.1 (3) Ptl c1 Pt3 78.8 (3)
Pt3 P31 ClOl 120.1 (3) Ptl c1 01 131.8 (6)
c3 P31 c91 104.1 (4) Pt2 c1 Pt3 77.6 (3)
c3 P31 ClOl 104.0 (4) Pt2 c1 01 133.1 (7)
c91 P31 ClOl 104.9 (4) Pt3 c1 01 134.9 (7)
Pt3 P32 c4 110.3 (3) P12 c2 P2 1 109.0 (4)
Pt3 P32 Clll 119.2 (3) P22 c3 P31 110.0 (4)
Pt3 P32 c121 110.1 (3) P11 c4 P32 112.8 (4)
c4 P32 Clll 103.3 (4)
settle this point, that the above argument is oversimplified, Preparation of [Pt(O@CF,),(dppm)]. [F'tC12(dppm)](5.131
and it should be recognized that greater steric effects would mmol) and [Ag02CCH3](10.244 mmol) were reacted in acetone
be observed if the CO ligand adopted a p2-bridging posi- (50 mL) in the presence of excess CF3COOH (15 mL). The
tion. However, we suggest that both steric and electronic suspension was stirred for 0.5 h at room temperature under Nz,
then heated briefly at 60 "C, and then allowed to cool for 1 h.
effects probably favor the unique Pt&-CO) linkage found The solution was then filtered, and the solvent was evaporated
experimentally for complex 2. from the filtrate under vacuum to give an oil. The oil was then
dissolved in acetone (5C-100 mL), and excess pentane was added
Experimental Section to precipitate a white crystalline solid: yield 92%; mp 200-210
Infrared spectra were recorded as Nujol mulls using a B e c k " "C dec; 'H NMR [(CD3)2CO]6 5.00 [t, ,J(PH) = 12, 3J(PtH) =
Acculab 4 spectrometer. 'H NMR and lHI3lP}NMR spectra were 88 Hz, CH2P2];,'P NMR [(CD3),C0] 6 -67.7 [s, 'J(PtP) = 3360
recorded on a Varian XL-100 NMR spectrometer. 31Pand lg5Pt Hz]. Anal. Calcd for [Pt(CF3COJz(dppm)]: C, 43.24; H, 2.75.
NMR spectra were recorded on a Varian XL-300 NMR spec- Found: C, 43.00; H, 2.92.
trometer. References were Mel% ('H), (Me0)3P0 (31P),and Preparation of [Pt3(~3-CO)(~-d~~m)31[CF3C0212. [Pt-
aqueous K2[PtC1,] (lg5Pt). (02CCF3)2(dppm)](1.319 mmol) and CO (4 atm) were reacted
A Platinum Complex Containing a Triply Bridging Carbonyl Organometallics, Vol. 5, No. 2, 1986 347

Table 11. Positional Parameters and Their Estimated Standard Deviationsa

atom X Y 2 B , A2 atom X Y z B , A2
Ptl 0.00260 (2) 6.26436 (2) 0.11090 (3) 2.166 (8) C52 0.0610 (8) 0.1162 (5) 0.4012 (8) 4.5 (2)*
Pt2 0.14305 (2) 0.22463 (2) 0.20046 (3) 2.159 (8) c53 0.0927 (9) 0.0800 (6) 0.4618 (9) 5.7 (3)*
Pt3 0.16857 (2) 0.26799 (2) 0.04172 (3) 2.168 (8) c54 0.1723 (9) 0.1087 (6) 0.547 (1) 6.3 (3)*
P1 0.2588 (3) 0.5404 (2) 0.2445 (3) 5.37 (9) c55 0.2204 (8) 0.1720 (5) 0.5768 (9) 5.5 (3)*
P2 0.7962 (3) 0.9755 (2) 0.1938 (3) 6.3 (1) C56 0.1915 (8) 0.2102 (5) 0.5177 (8) 4.6 (3)*
P11 -0.0578 (2) 0.3181 (1) 0.0049 (2) 2.52 (6) C61 0.1159 (6) 0.3095 (4) 0.4269 (6) 2.3 (2)*
P12 -0.1010 (2) 0.2438 (1) 0.2201 (2) 2.68 (6) C62 0.0838 (7) 0.3224 (5) 0.5175 (8) 3.8 (2)*
P21 0.0809 (2) 0.2275 (1) 0.3447 (2) 2.53 (6) C63 0.1114 (7) 0.3862 (5) 0.5781 (8) 4.4 (2)'
P22 0.2843 (2) 0.1951 (1) 0.2213 (2) 2.45 (6) C64 0.1695 (8) 0.4350 (5) 0.5499 (8) 4.6 (2)*
P31 0.3361 (2) 0.2729 (1) 0.0738 (2) 2.61 (6) C65 0.2012 (7) 0.4227 (5) 0.4611 (8) 4.2 (2)*
P32 0.1265 (2) 0.3126 (1) -0.0836 (2) 2.58 (6) C66 0.1738 (7) 0.3601 (4) 0.3980 (7) 3.2 (2)*
F11 0.2142 (6) 0.4647 (3) 0.2201 (6) 8.1 (2) C71 0.2463 (6) 0.1114 (4) 0.2120 (7) 2.9 (2)*
F12 0.3178 (6) 0.5473 (3) 0.3584 (5) 7.7 (2) C72 0.2644 (8) 0.0888 (5) 0.2966 (8) 4.6 (3)*
F13 0.3112 (7) 0.6141 (3) 0.2611 (6) 9.9 (3) c73 0.2230 (8) 0.0217 (5) 0.2854 (9) 5.7 (3)*
F14 0.1991 (6) 0.5326 (4) 0.1317 (5) 8.5 (2) c74 0.1634 (8) -0.0186 (5) 0.1940 (9) 5.5 (3)*
F15 0.3543 (6) 0.5290 (4) 0.1995 (7) 9.8 (3) c75 0.1439 (9) 0.0022 (6) 0.109 (1) 6.4 (3)*
F16 0.1685 (6) 0.5486 (5) 0.2857 (6) 11.8 (3) C76 0.1830 (8) 0.0674 (5) 0.1192 (9) 5.2 (3)*
F21 0.7856 (7) 1.0376 (4) 0.2601 (8) 12.0 (3) C81 0.3879 (6) 0.2355 (4) 0.3355 (7) 2.8 (2)*
F22 0.7107 (7) 0.9667 (5) 0.1003 (7) 12.0 (3) C82 0.3868 (7) 0.2879 (5) 0.4094 (8) 4.2 (2)*
F23 0.8106 (6) 0.9129 (4) 0.1265 (7) 9.5 (3) C83 0.4680 (8) 0.3196 (5) 0.4988 (8) 4.8 (3)*
F24 0.8854 (7) 0.9807 (4) 0.2850 (6) 11.9 (3) C84 0.5452 (8) 0.2951 (6) 0.5129 (9) 5.5 (3)*
F25 0.7159 (7) 0.9332 (1) 0.2394 (6) 9.9 (8) C85 0.5502 (9) 0.2461 (6) 0.4434 (9) 5.7 (3)*
F26 0.8764 (7) 1.0198 (4) 0.1506 (6) 9.5 (3) C86 0.4694 (7) 0.2143 (5) 0.3509 (8) 4.2 (2)*
01 0.0087 (5) 0.1374 (3) -0.0072 (5) 3.6 (2) c91 0.4204 (6) 0.3395 (4) 0.1846 (7) 2.7 (2)*
c2 -0.0603 (6) 0.1969 (4) 0.3010 (7) 3.1 (2) C92 0.3838 (7) 0.3872 (5) 0.2294 (8) 3.8 (2)*
co 0.3426 (6) 0.2015 (4) 0.1098 (7) 3.1 (2) c93 0.4491 (8) 0.4377 (5) 0.3160 (9) 5.4 (3)*
c4 0.0466 (6) 0.3605 (4) -0.0456 (7) 2.9 (2) c94 0.5448 (9) 0.4386 (6) 0.3545 (9) 5.9 (3)*
c11 -0.1077 (6) 0.3799 (4) 0.0588 (7) 2.7 (2)* c95 0.5815 (8) 0.3936 (5) 0.3105 (9) 5.3 (3)*
c12 -0.0424 (7) 0.4410 (5) 0.1150 (8) 4.2 (2)* C96 0.5188 (7) 0.3422 (5) 0.2235 (8) 4.1 (2)*
C13 -0.0780 (8) 0.4874 (5) 0.1659 (9) 5.3 (3)* ClOl 0.4034 (6) 0.2744 (4) -0.0289 (7) 3.0 (2)*
C14 -0.1808 (8) 0.4720 (5) 0.1593 (8) 4.8 (3)* c102 0.4649 (7) 0.3324 (5) -0.0367 (8) 4.3 (2)*
C15 -0.2478 (8) 0.4122 (5) 0.1055 (9) 5.4 (3)* C103 0.5150 (8) 0.3339 (5) -0.1159 (9) 5.3 (3)*
C16 -0.2106 (7) 0.3658 (5) 0.0543 (8) 4.2 (2)* C104 0.5024 (8) 0.2780 (5) -0.1865 (9) 5.2 (3)*
c21 -0.1583 (6) 0.2647 (4) -0.1084 (6) 2.5 (2)* C105 0.4399 (8) 0.2204 (5) -0.1832 (8) 4.8 (3)*
c22 -0.2026 (7) 0.2905 (5) -0.1797 (7) 3.7 (2)* C106 0.3897 (7) 0.2184 (5) -0.1040 (8) 3.9 (2)*
C23 -0.2773 (8) 0.2496 (5) -0.2673 (8) 4.8 (3)* Clll 0.2268 (6) 0.3675 (4) -0.1181 (7) 3.0 (2)*
C24 -0.3085 (8) 0.1849 (5) -0.2832 (9) 5.4 (3)* c112 0.2867 (7) 0.4257 (5) -0.0443 (8) 4.0 (2)*
C25 -0.2677 (8) 0.1590 (5) -0.2143 (9) 5.5 (3)* C113 0.3680 (8) 0.4677 (5) -0.0673 (9) 5.1 (3)*
C26 -0.1907 (7) 0.1999 (5) -0.1247 (7) 3.6 (2)* C114 0.3898 (8) 0.4523 (5) -0.1609 (9) 5.6 (3)*
C31 -0.1186 (6) 0.3086 (4) 0.3125 (7) 3.1 (2)* C115 0.3342 (9) 0.3959 (6) -0.2311 (9) 5.8 (3)*
C32 -0.1802 (7) 0.2957 (5) 0.3795 (8) 4.3 (2)* C116 0.2509 (8) 0.3532 (5) -0.2135 (8) 4.6 (3)*
c33 -0.1871 (8) 0.3466 (5) 0.4558 (9) 5.3 (3)* c121 0.0520 (6) 0.2502 (4) -0.2036 (7) 3.0 (2)*
c34 -0.1362 (8) 0.4075 (5) 0.4610 (8) 4.8 (3)* c122 0.0617 (7) 0.1899 (5) -0.2180 (8) 4.2 (2)*
c35 -0.0781 (8) 0.4208 (5) 0.3931 (8) 4.7 (3)* C123 0.0018 (8) 0.1392 (6) -0.3094 (9) 5.6 (3)*
C06 -0.0670 (7) 0.3712 (4) 0.3191 (7) 3.4 (2)* C124 -0.0623 (8) 0.1525 (6) -0.3807 (9) 5.5 (3)*
C41 -0.2280 (6) 0.1931 (4) 0.1427 (7) 2.9 (2)* C125 -0.0720 (8) 0.2099 (5) -0.3680 (9) 5.1 (3)*
C42 -0.2474 (8) 0.1298 (5) 0.0920 (9) 5.1 (3)* C126 -0.0132 (7) 0.2612 (4) -0.2785 (7) 3.5 (2)*
c43 -0.3417 (9) 0.0906 (6) 0.022 (1) 6.6 (3)* O(S1) 0.705 (1) 0.1391 (8) 0.415 (1) 18.9 (6)*
c44 -0.4141 (9) 0.1199 (6) 0.006 (1) 6.8 (3)* C(S2) 0.636 (2) 0.081 (1) 0.373 (2) 21 (1)*
c45 -0.3968 (9) 0.1829 (6) 0.051 (1) 6.5 (3)* C(S3) 0.563 (2) 0.067 (1) 0.271 (2) 16.1 (8)*
C46 -0.3024 (7) 0.2198 (5) 0.1228 (8) 4.3 (2)* C(S4) 0.643 (2) 0.039 (1) 0.437 (2) 17.2 (9)*
C51 0.119 ( 7 ) 0.1818 (4) 0.4295 ( 7 ) 3.2 (2)*
Atoms with an asterisk were refined isotropically. Anisotropically refined atoms are given in the form of the isotropic equivalent thermal
parameter defined as (4/3)[a2B(l,l)+ b2B(2,2)+ c2B(3,3) + ab(cos 7)B(1,2) + ac(cos @)B(1,3)+ bc(cos a)B(2,3)].

in a Parr pressure reactor (300-mL capacity) using methanol (50
mL) and distilled water (4 mL), which had initially been purged
with Nz, as solvent. The system was allowed to react for 71 h a t
100 "C. At 15-h intervals, the pressure reactor was cooled and
a fresh CO atmosphere was introduced. After this period the
system was cooled to room temperature, the reactor was opened,
and the solution was filtered. The solvent was evaporated from
the filtrate under vacuum to give the crude product as an orange
solid, yield 97.5%.
A sample was purified by recrystallization from an acetone-
pentane solvent system and characterized by elemental analysis.
IR: 1750 cm-' [u(CO)]. 'H NMR ((CD3)2CO): 6 5.85, 5.56 [m,
2J(HaHb)= 14, ,J(PtHa) = 52, 3J(PtHb)= 16 Hz, CHaHbP2]. 31P
NMR [(CD,)&O]: 6 -15.1 [s, 'J(PtP) = 3720, 'J(PP) = 170 Hz,
31P]. 195PtN M R 6 -2685 [t, 'J(PtP) = 3740, 'J(PtPt) == 380 Hz].
Anal. Calcd for [Pt3(CO)(dppm)3][CF3COz]2-(CH3)zCO: C, 48.6;
H, 3.5. Found: C, 49.0; H, 3.9.
Preparation a n d Crystal S t r u c t u r e Analysis of [Pt3(p3-
& . ~ P S ( ~ ~ - C O ) G - ~ P P ~ ) ~ I [=C2048;
C O ) ( ~ - ~ P P ~ ) ~ ] [ P FCrude
(0.334 mmol) was reacted with excess NH4[PF,] (8.190 mmol) in
methanol (10 mL). Upon addition of the NH4[PFB]solution a
flocculent orange precipitate formed. This product was filtered,
washed with methanol (1 mL), and dried in vacuo: yield 82%;
mp 275-285 "C dec. Anal. Calcd for [~GL3-CO)GL-dppm)31[PF612:
C, 44.39; H, 3.24. Found: C, 44.69; H, 3.52. Single crystals of
the acetone solvate were grown as small red plates from ace-
tone-pentane by slow diffusion: IR 1765 cm-' [v(CO)]. 'H NMR
[(CD,),CO]: 6 6.26, 5.66 [m, %T(HnHb)= 14, 3J(PtHa) = 72,
3J(PtHb)= 14 Hz, CHaHbPz]. 31PNMR [CD,CO]: 6 -6.7 [s,
'J(PtP) = 3710, 3J(PP)= 140 Hz, 31P]. Ig5PtN M R 6 -2893 [t,
'J(PtP) = 3730, 'J(PtPt) = 540 Hz].
For the X-ray data collection a small crystal was selected and
coated with thin layers of epoxy resin; preliminary studies had
shown that uncoated crystals decayed rapidly in the X-ray beam.
Crystal d a t a (at 21 "C) for [Pt3(p-CO)(p-dppm)3][PF6]2*
(CH3)&O: C79H72F1202P8Pt3; M,= 2114.5, triclinic, a = 14.090
(2) A, b = 22.711 (4) A, c = 13.637 (4) A; a = 103.43 (2)", p = 99.52
(2)O, y = 106.72 (1)"; U = 3937 (4) A3;2 = 2, D d d = 1.784; F(000)
F ~ CMo I ~radiation, X = 0.71069 A; ~ ( M KLY)
~ ~Ka o = 56.1 cm-';
space group P1 or Pi;Pi chosen and confirmed by the analysis.
348 Organometallics 1986, 5, 348-355
Accurate cell dimensions and crystal orientation matrix were
determined on a CAD4 diffractometer by a least-squarea treatment
of 25 reflections with 0 in the range 10-15'. The intensities of
reflections with h, -13 to +13, k, -21 to +21, and 1,0 to +13, with
2' < 0 < 20' were measured by the w-26 method using gra-
phite-monochromatized Mo K a radiation. The intensities of three
reflections chosen as standards were monitored every 0.83 h and
showed no evidence of crystal decay.
The intensities of 8060 reflections were measured of which 7318
were unique after averaging. Of these 6234 and I > 3u(I) and
were used in the structure solution and refinement. Data were
corrected18 for Lorentz and polarization effects and later for
absorption. The crystal used for the data collection measured
0.10 X 0.20 X 0.43 mm; the maximum and minimum values of
the transmission coefficients are 0.601 and 0.311, respectively.
Structure Solution and Refinement. The coordinates of
the three Pt atoms were deduced from a three-dimensional
Patterson function computed with data which had not been
corrected for absorption; the remaining non-hydrogen atoms of
the cation and anions were located from neccessive rounds of
structure factor and difference electron density maps. Initial
isotropic full-matrix refinement of the atoms was followed by five
cycles in which the non-phenyl atoms were allowed anisotropic
vibration. A difference map computed at this stage showed clearly
that acetone of solution had been entrapped in the crystal lattice;
maxima consistent with many of the hydrogen atoms of the
structure were also present. The composition of the unit cell
having now been established, the data were corrected for ab-
sorption. In the final rounds of full-matrixcalculations the solvate
0 and C atoms and the phenyl C atoms were allowed isotropic
vibration, all other non-hydrogen atoms were allowed to vibrate
anisotropically,and the 66 hydrogens of the cation were positioned
(18) All calculations were made on a PDP-11/73 computer using the
on geometrical grounds (C-H = 0.95 A) and included in the
calculation (with an overall Bi, of 5.0 A') but not refined. The
acetone of solvation is very loosely held in the lattice (average
B , for acetone atoms 18 A2), and no allowance was made for the
six acetone hydrogens.
Refinement converged with R = CllFol - IFcll/CIFoI = 0.035
and R, = (xw(lFol- lFc1)2/~wlFo12)1/2 = 0.046 for the 6234 ob-
served reflections; R = 0.044 for all reflections. The number of
variables in the final rounds of refinement was 557, and the
"goodness of fit" value was 1.50. The maximum shift/error ratios
were 0.02 for the x coordinate of atom C93 and 0.01 for the Biso
parameter of atom C103. A final difference map computed at
the end of the refinement calculations had three maxima greater
than 0.3 e A-3 (0.6-1.3 e A-3) near the Pt atoms but no chemically
significant features. In the refinement calculations, scattering
factors and anomalous dispersion corrections were taken from
ref 19;the weighting scheme was of the form w = 1/[2(F0) + 0.05
(F,2)1.
Principal dimensionsfor the structure are summarized in Table
I. Table I1 lists the final fractional coordinates of the non-hy-
drogen atoms with their estimated standard deviations. Tables
of all bond lengths and angles, thermal parameters, calculated
hydrogen coordinates, and mean plane data and a structure factor
listing are available as supplementary material.
Acknowledgment. Financial support from N.S.E.R.C.
(Canada) t o G.F. and R.J.P. is gratefully acknowledged.
Supplementary Material Available: Tables of all bond
lengths and angles, thermal parameters, calculated hydrogen
coordinates, and mean plane data and a listing of structure am-
plitudes (87 pages). Orderinginformation is given on any current
masthead page.
~~~~

SDP-PLUS system, (B.A. Frenz and Associates, Inc., College Station, TX (19) "International Tables for X-ray Crystallography";The Kynoch
77840, and Enraf-Nonius, Delft, Holland). Press, Birmingham, England, 1974; Vol. IV.

Metallocyclic Palladium( I I ) Complexes Possessing Six- and

Seven-Membered Rings:' Synthesis and Structural
Characteristics
George R. Newkome,' Garry E. Kiefer, Yves A. Frere,2aMasayoshi Onishi,2bVinod K. Gupta,
and Frank R. Fronczek
Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803- 1804
Received June 10, 1985

The syntheses of several new cyclometalated Pd(I1) complexes, which contain either phenanthroline
or bipyridine moieties, are described. These complexes achieve partial coordination to the metal core via
an sp3carbon anionic bond(s) and form fused cyclic ring systems with overall cis geometry. The dipyridyl
ethylenic and ketonic ligands undergo facile cyclometalation to generate the symmetric 5.7.5 and 5.6.5
complexes, respectively; in contrast, the potentially tetracoordinate 6.5.6 ligand systems available with
phenanthroline and bipyridine yielded only a single C-Pd bond. The single-crystal X-ray structural analyses
of selected complexes have afforded insight into the molecular features responsible for precluding generation
of dual C-Pd bonds in the 6.5.6 system.

Introduction
Up t o this point, our interest in metallocyclic palladi-
um(I1) complexes has been limited primarily to 2,2'-bi-
pyridine- and 1,lo-phenanthroline-based ligands capable
of forming a cis 5.5.5-cumulated ring ~ y s t e m . ~These
C z 5 5 5 cumulated r i n g system
(1) Chemistry of Heterocyclic Compounds series. Part 121.
(2) (a) On leave from Centre de Recherche sur lea Macromolecules, prototypes were designed specifically for the encapsulation
Strasbourg, France, 1982-1983. (b) On leave from Nagasaki University, of square-planar transition-metal ions and, with the ex-
Nagasaki, Japan, 1982-1983. ception of the phenanthroline derivatives, have demon-
(3) Newkome, G. R.; Puckett, W. E.; Kiefer, G. E.; Gupta, V. K.;
Fronczek, F. R.; Pantaleo, D. C.; McClure, G. L.; Simpson, J. B. Deutsch, strated a propensity for generating very stable tetradentate
W. A. Inorg. Chem. 1985, 24, 811. complexes in which partial coordination is achieved via sp3
0276-7333/86/2305-0348$01.50/0 0 1986 American Chemical Society