P-C bond cleavage of phosphorus-bridged [1]ferrocenophane coordinated to the [Cp(CO)2Fe]+ fragment

Article abstract of DOI:10.1021/om9507585

An iron complex with (1,1′-ferrocenediyl)phenylphosphine (FCPP) as a ligand, [Cp(CO)₂Fe-(FCPP)]⁺, was prepared, and its PF₆^- salt was subjected to X-ray crystal structure analysis. Photoirradiation of the PF₆^- salt resulted in Cp ring migration from a P to an Fe atom. Addition of H₂O or (n-Bu)₄NF to the reaction mixture gave an isolable complex, formulated as [Cp(CO)Fe(C₅H₄FeC₅H₄PFPh)]. The structure for one of the racemic isomers was determined with X-ray analysis. This isomer was a kinetic product and isomerized to its thermodynamically stable epimer in the presence of an F^- anion.

Full text of DOI:10.1021/om9507585

Organometallics 1996, 15, 1093-1100
1093
Articles
P -C Bon d Clea va ge of P h osp h or u s-Br id ged
[1]F er r ocen op h a n e Coor d in a ted to th e [Cp (CO)2F e]+
F r a gm en t
Tsutomu Mizuta,† Tomoaki Yamasaki,† Hiroshi Nakazawa,*,† and
Katsuhiko Miyoshi*,‡
Coordination Chemistry Laboratories, Institute for Molecular Science, Myodaiji, Okazaki 444,
J apan, and Department of Chemistry, Faculty of Science, Hiroshima University, Kagamiyama,
Higashi-Hiroshima 739, J apan
Received September 25, 1995X
An iron complex with (1,1′-ferrocenediyl)phenylphosphine (FCPP) as a ligand, [Cp(CO)2Fe-
(FCPP)]+, was prepared, and its PF6- salt was subjected to X-ray crystal structure analysis.
-
Photoirradiation of the PF6 salt resulted in Cp ring migration from a P to an Fe atom.
Addition of H2O or (n-Bu)4NF to the reaction mixture gave an isolable complex, formulated
as [Cp(CO)Fe(C5H4FeC5H4PFPh)]. The structure for one of the racemic isomers was
determined with X-ray analysis. This isomer was a kinetic product and isomerized to its
thermodynamically stable epimer in the presence of an F- anion.
In tr od u ction
atom-bridged [1]ferrocenophane.1a,d,7-11 Figure 1 shows
a phosphorus-bridged [1]ferrocenophane. The two Cp
rings are known to be considerably tilted (ca. 27°). Since
the ferrocenophane has lone-pair electrons on the
phosphorus, it may serve as a ligand toward a transition
metal. Several complexes (1-4)1b,12 possessing a phos-
phorus-bridged [1]ferrocenophane as a ligand have been
synthesized. However, their reactivities have not yet
been examined.
The ring-opening reaction of phosphorus-bridged [1]-
ferrocenophane provides an important synthetic route
to not only monomeric but also oligomeric and polymeric
ferrocenylphosphine derivatives.1,2 Most of the reac-
tions involve P-C bond cleavage by RLi. Treatment of
phosphorus-substituted lithioferrocenes thus prepared
with a variety of electrophiles leads to 1,1′-disubstituted
ferrocenes. Thermal ring-opening reactions have also
been used3,4 in some cases, though thermolysis has
commonly been employed for the conversion of silicon-
bridged [1]ferrocenophanes into polymeric silafer-
rocenes.5,6 The driving force of these ring-opening
reactions comes from the ring strain present in a single-
† Institute for Molecular Science.
‡ Hiroshima University.
X Abstract published in Advance ACS Abstracts, J anuary 1, 1996.
(1) (a) Seyferth, D.; Withers, H. P., J r. J . Organomet. Chem. 1980,
185, C1. (b) Seyferth, D.; Withers, H. P., J r. Organometallics 1982, 1,
1275. (c) Withers, H. P., J r.; Seyferth, D.; Fellmann, J . D.; Garrou, P.
E.; Martin, S. Organometallics 1982, 1, 1283. (d) Fellmann, J . D.;
Garrou, P. E.; Withers, H. P., J r.; Seyferth, D.; Traficante, D. D.
Organometallics 1983, 2, 818.
(2) (a) Butler, I. R.; Cullen, W. R.; Einstein, F. W. B.; Rettig, S. J .;
Willis, A. J . Organometallics 1983, 2, 128. (b) Butler, I. R.; Cullen, W.
R. Organometallics 1984, 3, 1846. (c) Butler, I. R.; Cullen, W. R.;
Einstein, F. W. B.; Willis, A. C. Organometallics 1985, 4, 603. (d)
Butler, I. R.; Cullen, W. R. Can. J . Chem. 1983, 61, 147. (e) Butler, I.
R.; Cullen, W. R. Organometallics 1986, 5, 2537.
We are interested in the reactivity of a phosphorus-
bridged [1]ferrocenophane coordinated to a transition
metal. Since P-C bond activation by an organometallic
(3) Cullen, W. R.; Rettig, S. J .; Zheng, T.-C. J . Organomet. Chem.
1993, 452, 97.
(7) Stoeckli-Evans, H.; Osborne, A. G.; Whiteley, R. H. Helv. Chim.
Acta 1976, 59, 2402.
(4) Honeyman, C.; Foucher, D. A.; Mourad, O.; Rulkens, R.; Man-
ners, I. Polymer Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1993, 34
(1), 330.
(5) (a) Manners, I. Adv. Organomet. Chem. 1995, 37, 131. (b)
Foucher, D.; Ziembinski, R.; Petersen, R.; Pudelski, J .; Edwards, M.;
Ni, Y.; Massey, J .; J aeger, C. R.; Vancso, G. J .; Manners, I. Macro-
molecules 1994, 27, 3992.
(6) (a) Nguyen, M. T.; Diaz, A. F.; Dement’ev, V. V.; Pannell, K. H.
Chem. Mater. 1993, 5, 1389. (b) Nguyen, M. T.; Diaz, A. F.; Dement’ev,
V. V.; Pannell, K. H. Chem. Mater. 1994, 6, 952.
(8) Butler, I. R.; Cullen, W. R.; Rettig, S. J . Can. J . Chem. 1987, 65,
1452.
(9) Finckh, W.; Tang, B.-Z.; Foucher, D. A.; Zamble, D. B.; Ziem-
binski, R.; Lough, A.; Manners, I. Organometallics 1993, 12, 823.
(10) Broussier, R.; Da Rold, A.; Gautheron, B.; Dromzee, Y.; J eannin,
Y. Inorg. Chem. 1990, 29, 1817.
(11) Stoeckli-Evans, H.; Osborne, A. G.; Whiteley, R. H. J . Orga-
nomet. Chem. 1980, 194, 91.
(12) Butler, I. R.; Cullen, W. R.; Rettig, S. J . Organometallics 1987,
6, 872.
0276-7333/96/2315-1093$12.00/0 © 1996 American Chemical Society

1094 Organometallics, Vol. 15, No. 4, 1996
Mizuta et al.
Sch em e 1
also performed in THF, but some complicated reactions
took place and the products could not be identified.) The
reaction was followed by infrared spectra in the ν(CO)
region. The two absorptions due to 6 disappeared
almost completely after 1 h of irradiation, and a number
of new absorptions appeared in the lower frequency
area. The 31P{1H} NMR spectrum of the reaction
mixture also showed the complete disappearance of 6
and the appearance of new broad signals at over 200
ppm and under 50 ppm. Several attempts to isolate the
products from the reaction mixture were unsuccessful.
We, accordingly, tried to change the cationic species
assumed to be formed into more stable species by
addition of a nucleophile such as (n-Bu)4NF or water.
In both cases, the 31P{1H} NMR spectrum turned out
to consist of four sharp signals above 200 ppm and a
multiplet assigned to PF6- as the major signals. Puri-
fication with an Al2O3 column led to the isolation of a
red crystalline complex, 8. Complex 8 was characterized
as shown below by spectroscopic data. Since the com-
plex has two chiral centers, Fe and P, it consists of the
two diastereomeric pairs RS/SR (8a ) and RR/SS (8b).
F igu r e 1. Distortions in phosphorus-bridged [1]ferro-
cenophane, defining angles R and â.
complex is known,13 it should be noteworthy to inves-
tigate what effect the coordination of the ferrocenophane
exerts on its ring-opening reactivity (a P-C bond
activation). We here focus on [Cp(CO)2Fe(FCPP)]+ (5),
where (1,1′-ferrocenediyl)phenylphosphine (FCPP) co-
ordinates through its phosphorus lone-pair electrons to
a cationic [Cp(CO)2Fe]+ fragment, and report our find-
ings that photochemical elimination of the carbonyl
ligand promotes the ring-opening reaction, or 1,2-shift,
of the Cp ring carbon from P to Fe with P-C bond
activation.
Resu lts a n d Discu ssion
P r ep a r a tion of 6. The reaction of FCPP with [Cp-
(CO)2Fe(THF)]PF6 in CH2Cl2 gave [Cp(CO)2Fe(FCPP)]-
PF6 (6) in excellent yield. The infrared spectrum in the
ν(CO) region showed two absorptions at 2056 and 2014
cm-1 in the CH2Cl2 solution, which are similar to those
(2059 and 2016 cm-1) for the PPh3 analog [Cp(CO)2Fe-
(PPh3)]PF6 (7a ).14 The 31P{1H} NMR spectrum of 6
showed a singlet at 77.7 ppm, which is 64.4 ppm lower
in magnetic field than that of free FCPP (13.3 ppm). A
similar downfield shift has been observed for 7a (-4.9
ppm for PPh3 to 61.5 ppm).15 The molecular structure
of 6 was confirmed with X-ray analysis and is shown in
Figure 2 (vide infra).
The intensities of the 31P{1H} NMR signals of the
isolated complex 8 indicate that the four signals ob-
served consist of two pairs of doublets at 220.8 and 242.5
ppm with the coupling constants 917.4 and 937.6 Hz,
respectively. These large coupling constants are con-
sistent with the presence of a P-F bond. The 19F{1H}
NMR spectrum also supports the notion that 8 has a
P-F bond: two doublets at -94.9 and -125.2 ppm with
the coupling constants 937.6 and 918.0 Hz, respectively.
The source of the fluorine atom in these reactions is
discussed later.
P h otoch em ica l Rea ction of 6. 6 was irradiated
with UV-vis light in CH2Cl2. (The photoreaction was
(13) Nakazawa, H.; Matsuoka, Y.; Nakagawa, I.; Miyoshi, K. Or-
ganometallics 1992, 11, 1385 and references therein.
(14) Literature values 2055 and 2010 cm-1
: (a) Treichel, P. M.;
Shubkin, R. L.; Barnett, K. W.; Reichard, D. Inorg. Chem. 1966, 5,
1177. (b) J ohnson, B. V.; Ouseph, P. J .; Hsieh, J . S.; Steinmetz, A. L.;
Shade, J . E. Inorg. Chem. 1979, 18, 1796.
The structure of 8 was determined by X-ray analysis.
A red single crystal was obtained after repeated recrys-
-
(15) Literature value of its BF4 salt in 1,2-dichloroethane 67.9
ppm: Schumann, H.; Eguren, L. J . Organomet. Chem. 1991, 403, 183.

Ring Opening of P-Bridged [1]Ferrocenophane
Organometallics, Vol. 15, No. 4, 1996 1095
tallization. Although the details of the structure will
be mentioned later, it is pertinent to note here that the
crystal obtained has an RS/SR configuration (8a ). The
31P{1H} spectrum of 8a showed one doublet at 220.8
ppm (1J P-F ) 917.4 Hz). Thus, the other doublet at
242.5 ppm (1J P-F ) 937.6 Hz) should be assigned to the
other pair of diastereomers, RR/SS (8b).
substituents.19 In contrast, 9 is not stable enough to
be detected, probably because the phosphenium phos-
phorus has one Fc and one Ph substituent. Since the
latter substituent makes the Lewis acidity of the phos-
phenium phosphorus greater than that of 10, because
of the poor electron-donating ability of a Ph substituent
compared with an Fc substituent, 9 may abstract a
-
fluoride anion from PF6
.
The abstraction of the
Mech a n ism of F or m a tion of [2]F er r ocen op h a n e
Com p lex 8 (8a ,b). Let us consider the reaction mech-
anism for the transformation from 6 to 8. The mecha-
nism we propose is shown in Scheme 1. First, one CO
ligand in 6 is activated by photolysis to generate a
coodinatively unsaturated 16-e complex. Then, a Cp
carbon in the FCPP fragment migrates from P to Fe
(1,2-shift) to relieve the strain, yielding the phosphe-
nium intermediate 9. The phosphenium species pro-
duced may be a strong Lewis acid, and so the phosphe-
fluoride by a metal-coordinated phosphenium has been
proposed in a few reactions;20,21 in eq 1, 11 reacts with
-
nium phosphorus may interact with a PF6 anion
-
through an F atom or abstract a fluoride from PF6
.
Such an abstraction of a fluoride leaves PF5, which is
trapped when F- or water is added.
Although the intermediate 9 could not be detected,
this mechanism seems to be plausible for the following
reasons. Photochemically induced loss of a CO followed
by a 1,2-shift has been reported for the complex [Cp-
(CO)2Fe-E1R2-E2R′3] (E1 and E2 ) Si and Ge) where the
E2R′3 group migrates from the E1 atom to the iron.16,17
Since the phosphorus-bridged [1]ferrocenophane is highly
strained as shown in Figure 2, where the Cp rings are
tilted by 25.0° (vide infra), the phosphorus-Cp bond
may be readily cleaved to become free from the strain.
The 1,2-shift of the Cp to the iron yields the cationic
phosphenium complex 9. A ferrocene unit, abbreviated
as Fc, has been utilized to stabilize a phosphenium.18,19
For example, 10 was reported to be a stable phosphe-
nium complex, where the phosphenium phosphorus
coordinates to an Fe(CO)4 fragment and has two Fc
(16) (a) Tobita, H.; Ueno, K.; Ogino, H. Chem. Lett. 1986, 1777. (b)
Tobita, H.; Ueno, K.; Ogino, H. Bull. Chem. Soc. J pn. 1988, 61, 2979.
(c) Ueno, K.; Tobita, H.; Shimoi, M.; Ogino, H. J . Am. Chem. Soc. 1988,
110, 4092. (d) Tobita, H.; Ueno, K.; Shimoi, M.; Ogino, H. J . Am. Chem.
Soc. 1990, 112, 3415. (e) Ueno, K.; Tobita, H.; Ogino, H. Chem. Lett.
1990, 369. (f) Ueno, K.; Hamashima, N.; Shimoi, M.; Ogino, H.
Organometallics 1991, 10, 959. (g) Koe, J . R.; Tobita, H.; Suzuki, T.;
Ogino, H. Organometallics 1992, 11, 150. (h) Koe, J . R.; Tobita, H.;
Ogino, H. Organometallics 1992, 11, 2479. (i) Takeuchi, T.; Tobita, H.;
Ogino, H. Organometallics 1991, 10, 835. (j) Ueno, K.; Hamashima,
N.;Ogino, H. Organometallics 1992, 11, 1435.
(17) (a) Pannell, K. H.; Cervantes, J .; Hernandez, C.; Cassias, J .;
Vincenti, S. Organometallics 1986, 5, 1056. (b) Pannell, K. H.; Rozell,
J . M.; Tsai, W.-M. Organometallics 1987, 6, 2085. (c) Pannell, K. H.;
Rozell, J . M.; Hernandez, C. J . Am. Chem. Soc. 1989, 111, 4482. (d)
Pannell, K. H.; Wang, L.-J .; Rozell, J . M. Organometallics 1989, 8, 550.
(e) Pannell, K. H.; Sharma, S. Organometallics 1991, 10, 954. (f)
Pannell, K. H.; Sharma, S. Organometallics 1991, 10, 1655. (g) J ones,
K. L.; Pannell, K. H. J . Am. Chem. Soc. 1993, 115, 11336. (h)
Hernandez, C.; Sharama, H. K.; Pannell, K. H. J . Organomet. Chem.
1993, 462, 259.
2 equiv of BF3‚OEt2 to afford the mono OR/F exchange
product 13.20 The reaction proceeds via the phosphe-
nium intermediate 12, which is not stable enough to be
detected. In eq 2, the NH2 of 14 is replaced by a
fluorine. Though the authors mentioned nothing about
the presence of the phosphenium species 15,21 it is
highly plausible that the reaction proceeds via a phos-
phenium intermediate in analogy to eq 1. Since the
(20) (a)Nakazawa, H.; Ohta, M.; Yoneda, H. Inorg. Chem. 1988, 27,
973. (b)Nakazawa, H.; Ohta, M.; Miyoshi, K.; Yoneda, H. Organome-
tallics 1989, 8, 638.
(18) Baxter, S. G.; Collins, R. L.; Cowley, A. H.; Sena, S. F. J . Am.
Chem. Soc. 1981, 103, 715.
(19) Baxter, S. G.; Collins, R. L.; Cowley, A. H.; Sena, S. F. Inorg.
Chem. 1983, 22, 3475.
(21) Bradley, F. C.; Wong, E. H.; Gabe, E. J .; Lee, F. L. Inorg. Chim.
Acta 1986, 120, L21.

1096 Organometallics, Vol. 15, No. 4, 1996
Ta ble 1. Cr ysta l a n d Refin em en t Da ta for Com p ou n d s 6 a n d 8a
Mizuta et al.
6
8a
(a) Crystal Data
chem formula
fw
C23H18F6Fe2O2P2
614.03
C22H18FFe2OP
460.05
cryst syst
unit cell dimens
a, Å
b, Å
c, Å
orthorhombic
monoclinic
12.127(3)
14.530(2)
27.030(3)
29.534(4)
7.256(1)
20.029(2)
120.943(9)
3681.0(8)
C2/c (No. 15)
1.660
â, deg
V, Å3
4762(1)
Pbca (No. 61)
1.713
space group
Dc, g cm-3
Z
8
8
F(000)
2464.0
1872.0
color, habit
cryst dimens
µ, cm-1
dark red, stick
0.60 × 0.42 × 0.40
14.18
red, plate
0.40 × 0.33 × 0.13
136.24
(b) Data Collection and Processing
Enraf-Nonius CAD4
Mo KR (graphite monochromated)
ω-θ
diffractometer
X-radiation
sacn mode
ω-scan width, deg
2θ limits, deg
data collected (hkl)
no. of rflns
Enraf-Nonius CAD4
Cu KR (graphite monochromated)
ω-θ
0.80 + 0.35 tan θ
0.50 + 0.15 tan θ
60
140
(002) to (17,20,38)
(-36,0,0) to (36,8,24)
total
7634
3869
unique (Rint
)
7634
3784 (0.112)
obsd
3630 (I > 3σ(I))
DIFABS (0.6538-1.0763)
2456 (I > 3σ(I))
DIFABS (0.6580-1.7504)
abs cor (transmissn factors)
(c) Structure Analysis and Refinement
structure soln
refinement
no. of params
weighting scheme
R, %
direct methods (SAPI91)
full-matrix least squares
direct methods (SAPI91)
full-matrix least squares
389
317
1/σ2(Fo)
0.054
0.051
1/σ2(Fo)
0.049
0.047
Rw, %
phosphenium phosphorus in 15 is a strong Lewis acid
because of the two Ph substituents, it abstracts the
fluoride anion to give 16. On the other hand, it was
reported that a fluoride could be abstracted with PF5
from a PF6- anion.22 If the acidity of 9 is much greater
than that of PF5, 9 abstracts the fluoride from its
counteranion, PF6-, to leave the weaker Lewis acid PF5
and the product 8. Neither such a product nor the
phosphenium species, however, could be observed in the
31P{1H} spectra after the irradiation. Therefore, we
suppose that 9 and PF5 are comparable in acidity and/
or that the reaction from 9 to the products is a fast
equilibrium. Once water is added to this equilibrium,
PF5 is immediately trapped to produce 8.
The reaction in Scheme 1 involves P-C bond activa-
tion by a transition-metal complex. Recently, many
results concerning P-C bond activation have been
reported,13 and some of the P-C activations have been
proposed to be attained by migration of an alkyl or an
aryl group in a phosphorus compound coordinated to a
transition metal to its transition metal. Although clear
evidence for this type of migration has not been given
in these reports, our present results afford unambiguous
evidence.
8a and 8b was examined. 8a isolated by recrystalliza-
tion was dissolved in CH2Cl2 at room temperature, and
the isomerization was monitored in the 31P{1H} spectra.
No reaction, however, was observed after 24 h. Then,
the same treatment was done in the presence of 1 equiv
of (n-Bu)4NF. The NMR intensity of the starting
diastereomer 8a decreased within 3 min to reach the
ratio of 1:5 for 8a :8b, which means that 8b is thermo-
dynamically more stable than 8a . This is reasonable
from the viewpoint of steric hindrance between the Cp
and the Ph groups on the two asymmetric centers. The
two bulky Cp and Ph groups on Fe(2) and P(1), respec-
tively, take a pseudo-eclipsed configuration in 8a as
shown in Figure 3, whereas they take a pseudo-gauche
configuration in 8b. Since the isomerization is acceler-
ated drastically in the presence of F-, it proceeds via
the associative mechanism as shown in the bottom path
of Scheme 2, where F- attacks the phosphorus atom
from the opposite side of the P-F bond to form a five-
coordinate species as an intermediate; nucleophilic
attack of a nucleophile such as F-, H-, or -OR to a
coordinating trivalent phosphorus has been reported to
give metallaphosphorane.23,24
In the reaction shown in Scheme 1, 8a is dominantly
produced as a kinetic product, whereas in the presence
of excess F-, i.e. (n-Bu)4NF, 8a is converted into the
thermodynamic product 8b. Such a kinetic effect is part
of the evidence for the phosphenium intermediate as
Isom er iza tion Rea ction betw een 8a a n d 8b. It
is noteworthy that the ratio of 8a to 8b is dependent
on the kind of additive. When (n-Bu)4NF was used as
an additive, the ratio was 1:5, whereas when water was
used, the ratio was 3:1. To elucidate the reason for this
difference, the isomerization between the diastereomers
(23) Mason, M. R.; Verkade, J . G. Organometallics 1992, 11, 2212.
(24) (a) Nakazawa, H.; Kubo, K.; Kai, C.; Miyoshi, K. J . Organomet.
Chem. 1992, 439, C42. (b) Nakazawa, H.; Kubo, K.; Miyoshi, K. J . Am.
Chem. Soc. 1993, 115, 5863.
(22) Brownstein, S.; Bornais, J . Can. J . Chem. 1968, 46, 225.

Ring Opening of P-Bridged [1]Ferrocenophane
Organometallics, Vol. 15, No. 4, 1996 1097
Ta ble 3. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 6 w ith Estim a ted Sta n d a r d Devia tion s in
P a r en th eses
Sch em e 2
Lengths
Fe(1)-C(1)
Fe(1)-C(3)
Fe(1)-C(5)
Fe(1)-C(7)
Fe(1)-C(9)
Fe(2)-P(1)
Fe(2)-C(23)
P(1)-C(6)
O(1)-C(22)
C(1)-C(2)
C(2)-C(3)
C(4)-C(5)
C(6)-C(10)
C(8)-C(9)
1.992(5)
2.084(7)
2.009(6)
2.021(7)
2.087(7)
2.201(2)
1.763(6)
1.837(5)
1.134(6)
1.442(7)
1.412(8)
1.411(8)
1.428(8)
1.39(1)
Fe(1)-C(2)
Fe(1)-C(4)
Fe(1)-C(6)
Fe(1)-C(8)
Fe(1)-C(10)
Fe(2)-C(22)
P(1)-C(1)
P(1)-C(11)
O(2)-C(23)
C(1)-C(5)
C(3)-C(4)
C(6)-C(7)
C(7)-C(8)
C(9)-C(10)
2.022(6)
2.088(7)
1.981(5)
2.078(7)
2.014(7)
1.773(6)
1.844(5)
1.807(5)
1.125(6)
1.444(8)
1.409(9)
1.444(7)
1.405(8)
1.413(9)
Ta ble 2. F in a l F r a ction a l Coor d in a tes a n d
Th er m a l P a r a m eter s for th e Non -Hyd r ogen Atom s
of 6
Angles
P(1)-Fe(2)-C(22)
C(22)-Fe(2)-C(23)
Fe(2)-P(1)-C(6)
C(1)-P(1)-C(6)
C(6)-P(1)-C(11)
P(1)-C(1)-C(5)
C(1)-C(2)-C(3)
C(3)-C(4)-C(5)
P(1)-C(6)-C(7)
C(7)-C(6)-C(10)
C(7)-C(8)-C(9)
C(6)-C(10)-C(9)
Fe(2)-C(23)-O(2)
97.7(2) P(1)-Fe(2)-C(23)
96.5(3) Fe(2)-P(1)-C(1)
118.0(2) Fe(2)-P(1)-C(11)
95.0(2) C(1)-P(1)-C(11)
103.2(2) P(1)-C(1)-C(2)
121.2(4) C(2)-C(1)-C(5)
108.4(6) C(2)-C(3)-C(4)
107.6(6) C(1)-C(5)-C(4)
119.8(4) P(1)-C(6)-C(10)
105.9(5) C(6)-C(7)-C(8)
109.4(6) C(8)-C(9)-C(10)
89.2(2)
117.3(2)
114.0(2)
106.8(2)
117.6(4)
105.5(5)
109.1(6)
109.4(6)
119.9(4)
107.9(6)
107.9(6)
a
atom
x
y
z
Beq
,
Å2
Fe(1)
Fe(2)
P(1)
P(2)
F(1)
F(2)
F(3)
F(4)
F(5)
0.12865(6)
0.04493(6)
0.1615(1)
0.2396(1)
0.1449(5)
0.2432(4)
0.1525(4)
0.3261(5)
0.2339(4)
0.3315(4)
-0.1594(3)
0.0913(4)
0.1500(4)
0.0446(5)
0.0630(6)
0.1773(6)
0.2311(5)
0.1496(5)
0.0458(6)
0.0680(6)
0.1814(7)
0.2326(6)
0.3046(4)
0.3674(5)
0.4762(6)
0.5222(6)
0.4617(6)
0.3519(5)
0.0135(7)
-0.0456(7)
0.0291(10)
0.1359(7)
0.1237(6)
-0.0778(5)
0.0721(5)
0.24833(6)
0.14101(5)
0.18209(9)
0.4187(1)
0.4234(4)
0.5258(2)
0.4269(3)
0.4111(4)
0.3120(3)
0.4110(4)
0.1561(4)
-0.0492(3)
0.3002(3)
0.3286(4)
0.3806(4)
0.3859(4)
0.3370(4)
0.1262(3)
0.1280(4)
0.1443(5)
0.1518(6)
0.1408(5)
0.1646(3)
0.2349(4)
0.2203(6)
0.1354(7)
0.0645(6)
0.0781(4)
0.2535(6)
0.1771(7)
0.1098(7)
0.1436(6)
0.2321(5)
0.1502(4)
0.0247(4)
0.99230(3)
0.84207(3)
0.90043(5)
0.69581(7)
0.7329(2)
0.6965(2)
0.6537(2)
0.7356(2)
0.6941(2)
0.6567(2)
0.8976(2)
0.8650(2)
0.9248(2)
0.9442(2)
0.9876(3)
0.9966(3)
0.9585(2)
0.9611(2)
0.9872(2)
1.0375(2)
1.0444(2)
0.9978(2)
0.8843(2)
0.8644(2)
0.8513(3)
0.8573(3)
0.8770(3)
0.8903(2)
0.7963(3)
0.7799(3)
0.7678(2)
0.7768(2)
0.7939(2)
0.8773(2)
0.8561(2)
4.88(2)
3.59(2)
3.47(3)
5.47(4)
16.1(2)
10.4(1)
12.3(2)
16.6(2)
12.1(2)
13.0(2)
8.2(1)
8.5(2)
4.4(1)
5.0(1)
6.2(2)
6.4(2)
5.3(2)
4.5(1)
5.4(2)
6.9(2)
7.3(2)
5.8(2)
3.9(1)
5.1(2)
6.3(2)
7.0(2)
6.6(2)
5.0(2)
6.8(2)
6.9(2)
7.7(3)
6.3(2)
5.7(2)
5.3(1)
5.0(1)
108.9(6) Fe(2)-C(22)-O(1) 176.4(5)
178.8(6)
F(6)
Ta ble 4. F in a l F r a ction a l Coor d in a tes a n d
Th er m a l P a r a m eter s for th e Non -Hyd r ogen Atom s
of 8a
O(1)
O(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
a
atom
x
y
z
Beq
,
Å2
Fe(1)
Fe(2)
P(1)
F(1)
O(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
0.69338(3)
0.55770(3)
0.61431(6)
0.5970(1)
0.5591(2)
0.6183(2)
0.6388(3)
0.6860(3)
0.6968(2)
0.6547(2)
0.6788(2)
0.6891(3)
0.7408(2)
0.7626(2)
0.7249(2)
0.6284(2)
0.6559(3)
0.6645(3)
0.6462(3)
0.6211(3)
0.6122(2)
0.5260(3)
0.5113(3)
0.4822(2)
0.4771(3)
0.5039(3)
0.5600(2)
0.1929(1)
0.1826(1)
0.0618(2)
-0.1434(5)
-0.1484(7)
0.2974(8)
0.2457(9)
0.3472(10)
0.4614(9)
0.4311(9)
0.0154(8)
-0.0815(9)
-0.0385(10)
0.0876(10)
0.1235(10)
0.1501(9)
0.0444(10)
0.0992(12)
0.2668(14)
0.3831(14)
0.3256(11)
0.4243(12)
0.4086(14)
0.2496(12)
0.1641(15)
0.2691(13)
-0.0158(9)
0.31384(5)
0.17131(5)
0.14673(8)
0.1112(2)
0.2530(3)
0.2644(3)
0.3449(4)
0.3936(4)
0.3463(4)
0.2681(4)
0.2286(3)
0.2982(3)
0.3580(4)
0.3277(4)
0.2478(4)
0.0756(3)
0.0504(4)
-0.0081(4)
-0.0418(4)
-0.0168(5)
0.0422(4)
0.1062(4)
0.1619(5)
0.1513(4)
0.0844(4)
0.0577(4)
0.2209(4)
1.77(2)
2.24(2)
2.23(3)
3.40(9)
5.1(1)
1.8(1)
2.5(1)
2.9(2)
3.0(2)
2.5(1)
2.1(1)
2.5(1)
2.7(1)
2.9(2)
2.5(1)
2.3(1)
3.0(2)
3.9(2)
4.6(2)
4.6(2)
3.4(2)
3.7(2)
4.3(2)
3.9(2)
5.0(2)
4.2(2)
3.0(2)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
a
Beq
)
8/3π2(U11(aa*)2 + U22(bb*)2 + U33(cc*)2 + 2U12aa*bb*
cos γ + 2U13aa*cc* cos â + 2U23 bb*cc* cos R).
shown at the top of Scheme 2. When PF6- attacks the
phosphenium phosphorus, which has a trigonal-planar
geometry, the approach from the CO side may be
preferable to that from the bulky Cp side, making 8a
the major kinetic product.
a
See footnote a in Table 2.
[Cp(CO)2Fe(PPh3)]Cl‚3H2O (7b)25 and that (2.240(1) Å)
in [Cp(CO)2Fe(PPh3)]{(NC)2CC(CN)C(CN)2} (7c; (NC)2-
CC(CN)C(CN)2 ) 1,1,2,3,3-pentacyanopropenide).26 The
Fe-CO distances (1.773(5) and 1.763(6) Å) are almost
the same as those in 7b,c (1.775(4) and 1.767(4) Å, and
1.778(5) and 1.774(7) Å, respectively), as expected from
X-r a y Str u ctu r es of 6 a n d 8a . Single crystals of 6
and 8a were obtained from CH2Cl2/Et2O. The cell
constants and the data collection parameters are sum-
marized in Table 1. The fractional coordinates and
important bond lengths and angles are listed in Tables
2-5.
(25) Riley, P. E.; Davis, R. E. Organometallics 1983, 2, 286.
(26) Sim, G. A.; Woodhouse, D. I.; Knox, G. R. J . Chem. Soc., Dalton
Trans. 1979, 629.
In 6, shown in Figure 2, the Fe(2)-P(1) distance
(2.201(2) Å) is slightly shorter than that (2.242(1) Å) in

1098 Organometallics, Vol. 15, No. 4, 1996
Mizuta et al.
Ta ble 6. Selected Str u ctu r a l Da ta for
(1,1′-F er r ocen ed iyl)p h en ylp h osp h in e (F CP P ) a n d
Ir on Com p lexes w ith F CP P a s a Liga n d
FCPP
[CpH(CO)-
[Cp(CO)2Fe-
(free ligand) Fe(FCPP)] (3) (FCPP)]PF6 (6)
P-Fe,a
Å
2.774(1)
1.849(5)
1.850(5)
26.9
32.3
2a
2.731(2)
1.837(6)
1.841(5)
25.4
33.9
12
2.693(2)
1.837(5)
1.844(5)
25.0
34.6
this work
P-C(Cp), Å
ring tilt, R, deg
â,b deg
ref
a
Distance between the bridging phosphorus atom and the iron
b
atom of the ferrocene unit. Average of the angles â1 and â2 in
Figure 1.
F igu r e 2. Crystal structure of [Cp(CO)2Fe(FCPP)]+ in 6
with the numbering scheme. Thermal ellipsoids are drawn
-
at 50% probability. PF6 was eliminated for clarity.
Ta ble 5. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 8a w ith Estim a ted Sta n d a r d Devia tion s
in P a r en th eses
Lengths
Fe(1)-C(1)
Fe(1)-C(3)
Fe(1)-C(5)
Fe(1)-C(7)
Fe(1)-C(9)
Fe(2)-P(1)
Fe(2)-C(22)
P(1)-C(6)
O(1)-C(22)
C(1)-C(5)
C(3)-C(4)
C(6)-C(7)
C(7)-C(8)
C(9)-C(10)
2.053(5)
2.051(6)
2.014(7)
2.009(6)
2.063(6)
2.157(2)
1.730(7)
1.795(6)
1.165(7)
1.422(8)
1.412(9)
1.446(7)
1.408(8)
1.427(8)
Fe(1)-C(2)
Fe(1)-C(4)
Fe(1)-C(6)
Fe(1)-C(8)
Fe(1)-C(10)
Fe(2)-C(1)
P(1)-F(1)
P(1)-C(11)
C(1)-C(2)
C(2)-C(3)
C(4)-C(5)
C(6)-C(10)
C(8)-C(9)
2.039(6)
2.039(7)
2.001(6)
2.072(6)
2.035(6)
1.985(5)
1.616(4)
1.796(6)
1.449(7)
1.427(9)
1.429(8)
1.442(8)
1.422(9)
Angles
P(1)-Fe(2)-C(1)
C(1)-Fe(2)-C(22)
Fe(2)-P(1)-C(6)
F(1)-P(1)-C(6)
C(6)-P(1)-C(11)
Fe(2)-C(1)-C(5)
C(1)-C(2)-C(3)
C(3)-C(4)-C(5)
Fe(1)-C(6)-P(1)
P(1)-C(6)-C(10)
C(6)-C(7)-C(8)
C(8)-C(9)-C(10)
Fe(2)-C(22)-O(1)
87.4(2)
93.4(3)
P(1)-Fe(2)-C(22)
Fe(2)-P(1)-F(1)
Fe(2)-P(1)-C(11)
F(1)-P(1)-C(11)
Fe(2)-C(1)-C(2)
C(2)-C(1)-C(5)
C(2)-C(3)-C(4)
C(1)-C(5)-C(4)
P(1)-C(6)-C(7)
C(7)-C(6)-C(10)
C(7)-C(8)-C(9)
C(6)-C(10)-C(9)
89.2(2)
111.6(1)
124.0(2)
97.4(2)
126.5(5)
104.2(5)
108.8(6)
111.7(6)
124.7(4)
107.8(5)
108.0(6)
106.5(6)
F igu r e 3. Molecular structure of 8a with the numbering
scheme. Thermal ellipsoids are drawn at 50% probability.
116.8(2)
100.2(2)
102.8(3)
128.9(4)
109.3(6)
106.0(6)
108.6(3)
123.7(5)
108.2(6)
109.5(6)
176.9(6)
and 6, respectively, indicating that the phosphorus atom
slightly approaches the iron atom in this order. The
shortening of the P-Fe(ferrocene) distance causes a
decrease of the tilt angle R and an increase of â, because
the bridging P-C (in Cp) bond distances are almost
constant. The reason for this shortening may come from
a weak interaction between the phosphorus atom and
the iron atom. Silver proposed, for some [1]ferro-
cenophanes on the basis of the Mo¨ssbauer data, a weak
interaction between a vacant d orbital of the bridging
phosphorus and a filled d orbital of the iron, though the
distance between them is considerably longer than that
of the normal Fe-P bonds.27 In the series of phosphorus-
bridged [1]ferrocenophanes in Table 6, the lone-pair
electrons of the phosphine are withdrawn more by the
cationic dicarbonyl fragment [Cp(CO)2Fe]+ than by the
neutral monocarbonyl fragment [Cp(CO)HFe]. Thus,
the phosphorus atom in [Cp(CO)2Fe(FCPP)]+ becomes
the most electron-deficient and may interact most
strongly with the iron atom. As a result, the phosphorus
atom is closer to the iron in the order free FCPP, [Cp-
(CO)HFe(FCPP)], and [Cp(CO)2Fe(FCPP)]PF6. Similar
structural deformation was observed for a series of
the ν(CO) frequencies of 6 and 7a . These structural and
spectroscopic similarities between [Cp(CO)2Fe(FCPP)]+
and [Cp(CO)2Fe(PPh3)]+ indicate that FCPP serves as
a donor ligand similarly to PPh3.
As shown in Figure 2 and Table 6, the two Cp rings
in the [1]ferrocenophane unit in 6 are considerably tilted
as expected. The dihedral angle, R, is 25.0°, which is
comparable to the value of 26.9° for the free ligand
FCPP.2a It is thus confirmed that the strain of the [1]-
ferrocenophane unit is almost intact when FCPP coor-
dinates to a metal, as previously described for [Cp(CO)-
HFe(FCPP)] (3), in which R is 25.4°.12 The structural
differences among FCPP, [Cp(CO)HFe(FCPP)] (3), and
[Cp(CO)2Fe(FCPP)]PF6 (6) in Table 6 give us an inter-
esting structural feature of the phosphorus-bridged [1]-
ferrocenophane. The distances between the bridging
phosphorus atom and the iron atom in the ferrocene unit
are 2.774(2), 2.731(2), and 2.693(2) Å for free FCPP, 3,
(27) Houlton, A.; Roberts, R. M. G.; Silver, J .; Drew, M. G. B. J .
Chem. Soc., Dalton Trans. 1990, 1543.

Ring Opening of P-Bridged [1]Ferrocenophane
Organometallics, Vol. 15, No. 4, 1996 1099
ally, the C5H4-Fe-P bond angles are 87.4(2) and
90.46(5)°, and the C5H4-P-Fe bond angles are 116.8-
(2) and 114.08(5)° for 8a and 17, respectively. As a
result, the bridging Fe-P group shifts slightly from the
symmetrical position to the upper side to enjoy the
preferred angle for each atom, making â1 considerably
smaller than â2.
Exp er im en ta l Section
Gen er a l Rem a r k s. All reactions were carried out under
an atmosphere of dry nitrogen using Schlenk tube techniques.
CH2Cl2 and ether were distilled from P2O5 and sodium metal,
respectively, and stored under an nitrogen atmosphere.
IR spectra were recorded on a Shimadzu FTIR-8100A
spectrometer. J EOL EX-270, EX-400, and LA-500 spectrom-
eters were used to obtain 1H, 13C, 19F, and 31P NMR spectra.
1H and 13C NMR data were referenced to (CH3)4Si, 19F NMR
data to CFCl3, and 31P NMR data to 85% H3PO4. A Shimadzu
GCMS QP-1000EX was used to obtain mass spectra.
F igu r e 4. Distortions in the [2]ferrocenophane unit of 8a .
â1 and â2 are the angles defined by the least-squares plane
of the C5 ring and C(1)-Fe(2) bond or C(6)-P(1) bond,
respectively.
P r ep a r a tion of 6. 6 was prepared from [Cp(CO)2Fe(THF)]-
PF6 and FCPP in a manner similar to that for [Cp(CO)2Fe-
{P(OMe)3}]PF6.29,30
[Cp(CO)2Fe(THF)]PF6 (1.43 g, 3.62 mmol) and FCPP (1.06
g, 3.63 mmol) were treated in 30 mL of CH2Cl2 at room
temperature. After the mixture was stirred for over 30 min,
removal of the solvent under reduced pressure yielded a brown
residue. After this was crushed into powder, it was washed
twice with 20 mL of ether and then dried in vacuo to give 6
(2.20 g, 3.58 mmol, 95%). 1H NMR (270 MHz, CDCl3): δ 4.42,
4.64, 4.78, and 4.94 (m, 8H, ferrocene), 5.25 (s, 5H, Cp), 7.57-
7.85 (m, 5H, Ph). 13C{1H} NMR (CD3COCD3): δ 19.3 (d, 1J C-P
) 27.5 Hz, ferrocene), 77.0 (d, J C-P ) 18.6 Hz, ferrocene), 77.7
(d, J C-P ) 3.4 Hz, ferrocene), 81.6 (d, J C-P ) 11.7 Hz,
ferrocene), 81.6 (d, J C-P ) 3.4 Hz, ferrocene), 89.9 (s, Cp), 130.3
(d, J C-P ) 10.3 Hz, Ph), 131.0 (d, J C-P ) 11.7 Hz, Ph), 133.5
silicon-bridged [1]ferrocenophanes, (R′C5H3FeC5H4)SiR2
(R ) Me, R′ ) H; R ) Ph, R′ ) H; R ) Cl, R′ ) CH-
(Me)NMe2), in which the distance between the silicon
and iron atom9 (2.690(3), 2.636(5), and 2.5931(1) Å for
R ) Me,9 Ph,7 Cl,8 respectively) decreases depending on
the electronegativity of R.
In 8a , shown in Figure 3, the ferrocene unit is bridged
by the Fe(2)-P(1) group. Fe(2) is surrounded by η5-Cp,
CO, η1-Cp, and the phosphorus ligand to make the well-
known piano-stool type geometry. Fe(2), Ph, η1-Cp, and
F(1) bond to P(1) to make a tetrahedral geometry. The
structure in Figure 4 shows a heteroatom-bridged [2]-
ferrocenophane unit. This unit is similar to that of the
previously reported 17,2b corresponding to a complex
formally formed by a replacement of F in 8a by Ph. The
tilt angles of the ferrocene unit are 11.7 and 11.5° for
8a and 17, respectively. Though these angles are
significantly reduced from the tilt angle of the parent
[1]ferrocenophane (for example, 25.0° for 6), their values
mean that the Fe-P bonds (2.157(2) and 2.116(5) Å for
8a and 17, respectively) are still short as a bridging part
of a strain-free ferrocene. Further reduction of the tilt
angle was observed for 18, in which R is 4.2° and the
Si-Si distance is 2.3535(9) Å.9,28
1
(d, J C-P ) 55.7 Hz, P-ipso-Ph), 133.6 (d, J C-P ) 3.4 Hz, Ph),
220.8 (d, 2J C-P ) 24.7 Hz, CO). 31P{1H} NMR (CH2Cl2): δ 77.7.
IR (ν(CO), CH2Cl2 solution): 2056, 2014 cm -1. Anal. Calcd
for C23H18F6Fe2O2P2: C, 44.99; H, 2.95. Found: C, 45.23; H,
3.17.
P h otor ea ction of 6 a n d Isola tion of th e P r od u ct 8. A
Pyrex Schlenk tube connected to a vent was charged with 6
(648 mg, 1.06 mmol) dissolved in 20 mL of CH2Cl2. Irradiation
was carried out in an ice-cooled bath with a 400 W medium-
pressure Hg arc lamp for 1 h. Then, 2 mL of water was added
to the solution. After it was stirred for a few minutes, the
solution was loaded on an Al2O3 column. An orange band
eluted with CH2Cl2 was collected. After removal of the solvent,
the residue was dried in vacuo to give a mixture of 8a and 8b
(100 mg, 0.237 mmol, 22%). Anal. Calcd for C22H18FFe2OP:
C, 57.44; H, 3.94. Found: C, 57.33; H, 4.10.
The diastereomeric mixture thus obtained was recrystallized
several times by addition of ether to the CH2Cl2 solution. The
crystals obtained were 8a . Spectroscopic data for 8a are as
follows. 1H NMR (270 MHz, CDCl3): δ 3.88, 3.92, 4.11, 4.28,
3
4.36, 4.47, and 5.25 (m, 8H, ferrocene), 4.55 (d, J H-P ) 1.3
Hz, 5H, Cp), 7.58-8.02 (m, 5H, Ph). 13C{1H} NMR (CDCl3):
δ 65.7 (d, J ) 24.2 Hz, ferrocene), 68.8 (d, J ) 8.1 Hz,
ferrocene), 72.0 (d, J ) 2.7 Hz, ferrocene), 72.7 (d, J ) 29.6
Hz, ferrocene), 72.8 (d, J ) 32.3 Hz, ferrocene), 73.2 (d, J )
12.1 Hz, ferrocene), 74.4 (s, ferrocene), 82.3 (s, ferrocene), 83.1
(s, Cp), 83.9 (s, ferrocene), 86.7 (dd, J ) 33.6 and 63.2 Hz,
P-ipso-ferrocene), 128.5 (d, J ) 10.7 Hz, Ph), 129.6 (dd, J )
4.8 and 12.1 Hz, Ph), 131.0 (s, Ph), 139.1 (dd, J ) 13.4 and
29.6 Hz, P-ipso-Ph), 221.3 (dd, J ) 4.0 and 43.1 Hz, CO).
Other distortion parameters, â1 and â2, reflect the
properties of the bridging atoms, as shown in Figure 4.
â1’s for 8a and 17 are 5.4 and 5.2°, respectively, whereas
â2’s are 16.3 and 13.1°, respectively. A piano-stool type
of transition-metal complex prefers a right angle for the
bond angles between the three legs, whereas a phos-
phorus atom tends to take a tetrahedral angle. Actu-
1
19F{1H} NMR (CH2Cl2): δ -94.39 (d, J F-P ) 918.0 Hz).
(29) Catheline, D.; Astruc, D. Organometallics 1984, 3, 1094.
(30) Nakazawa, H.; Kubo, K.; Tanisaki, K.; Kawamura, K.; Miyoshi,
K. Inorg. Chim. Acta 1994, 222, 123.
(28) Dement’ev, V. V.; Cervantes-Lee, F.; Parkanyi, L.; Sharma, H.;
Pannell, K. H.; Nguyen, M. T.; Diaz, A. Organometallics 1993, 12, 1983.

1100 Organometallics, Vol. 15, No. 4, 1996
Mizuta et al.
1
2
31P{1H} NMR (CH2Cl2): δ 220.8 (d, J P-F ) 917.4 Hz). IR
for compound 8a were obtained (Rw ) [∑w||Fo| - |Fc|| /
-1
∑w|Fo| ]1/2 and w ) 4Fo2/σ2(Fo)). All calculations were per-
2
(ν(CO), CH2Cl2 solution): 1936 cm
.
Spectroscopic data for 8b are as follows. 1H NMR (270 MHz,
CDCl3): δ 4.10, 4.18, 4.28, 4.41, 4.46, 4.50, and 5.00 (m, 8H,
ferrocene), 4.71 (d, 3J H-P ) 1.0 Hz, 5H, Cp), 7.45-7.79 (m, 5H,
Ph). 13C{1H} NMR (CDCl3): δ 68.7 (d, J ) 7.4 Hz, ferrocene),
70.1 (d, J ) 17.0 Hz, ferrocene), 70.1 (d, J ) 23.2 Hz,
ferrocene), 71.5 (d, J ) 2.5 Hz, ferrocene), 72.3 (d, J ) 9.8 Hz,
ferrocene), 73.3 (d, J ) 9.7 Hz, ferrocene), 74.0 (s, ferrocene),
82.0 (s, ferrocene), 83.0 (s, ferrocene), 83.1 (s, Cp), 87.1 (dd, J
) 17.0 and 42.8 Hz, P-ipso-ferrocene), 128.4 (d, J ) 9.7 Hz,
Ph), 130.2 (d, J ) 14.6 Hz, Ph), 131.5 (s, Ph), 142.7 (dd, J )
14.6 and 34.1 Hz, P-ipso-Ph), 220.9 (dd, J ) 4.9 and 31.7 Hz,
CO). 19F{1H} NMR (CH2Cl2): δ -125.21 (d, 1J F-P ) 937.6 Hz).
formed using teXsan33 with neutral atom scattering factors
from Cromer and Waber,34 ∆f and ∆f ′ values,35 and mass
attenuation coefficients.36 Anomalous dispersion coefficients
were included in Fc.
Ack n ow led gm en t. This work was supported by
Grants-in-Aid for Scientific Research (No. 07404037)
and Priority Area of Reactive Organometallics (No.
07216276) from the Ministry of Education, Science,
Sports and Culture of J apan.
1
31P{1H} NMR (CH2Cl2): δ 242.5 (d, J P-F ) 937.6 Hz). IR
Su p p or tin g In for m a tion Ava ila ble: Full listings of
atomic coordinates, anisotropic thermal parameters, bond
lengths, and bond angles for 6 and 8a (11 pages). This
material is contained in many libraries on microfiche, im-
mediately follows this article in the microfilm version of the
journal, can be ordered from the ACS, and can be downloaded
from the Internet; see any current masthead page for ordering
information and Internet access instructions.
-1
(ν(CO), CH2Cl2 solution): 1936 cm
.
X-r a y Str u ctu r e An a lyses of 6 a n d 8a . Crystallographic
and experimental details of X-ray crystal structure analyses
are given in Table 1. Suitable crystals of 6 and 8a were
mounted independently on an Enraf-Nonuis CAD-4 automatic
diffractometer. Data were collected at room temperature.
Intensities were corrected for Lorentz and polarization effects
in the usual manner. The structures were solved by a
combination of direct methods31 and Fourier synthesis32 and
refined by full-matrix least-squares calculations. All non-
hydrogen atoms were refined anisotropically, and hydrogen
atoms were treated isotropically. Final values of R ) 0.054
and Rw ) 0.051 for compound 6 and R ) 0.049 and Rw ) 0.047
OM9507585
(33) teXsan: Crystal Structure Analysis Package; Molecular Struc-
ture Corp. The Woodlands, TX, 1985, 1992.
(34) Cromer, D. T.; Waber, J . T. International Tables for X-ray
Crystallography; Kynoch Press: Birmingham, England, 1974; Vol. IV,
Table 2.2 A.
(35) Creagh, D. C.; McAuley, W. J . In International Tables for
Crystallography; Wilson, A. J . C., Ed.; Kluwer Academic: Boston, 1992;
Vol C, Table 4.2.6.8, pp 219-222.
(36) Creagh, D. C.; Hubbell, J . H. International Tables for Crystal-
lography; Wilson, A. J . C., Ed.; Kluwer Academic: Boston, 1992; Vol
C, Table 4.2.4.3, pp 200-206.
(31) SAPI91: Fan, H.-F. Structure Analysis Programs with Intel-
ligent Control; Rigaku Corp., Tokyo, J apan, 1991.
(32) DIRDIF92: Beurskens, P. T.; Admiraal, G.; Beurskens, G.;
Bosman, W. P.; Garcia-Granda, S.; Gould, R. O.; Smits, J . M. M.;
Smykalla, C. The DIRDIF Program System, Technical Report of the
Crystallography Laboratory; University of Nijmegen, Nijmegen, The
Netherlands, 1992.