Synthesis and reactivity of acylphosphine tetracarbonyl-iron complexes

Article abstract of DOI:10.1016/S0022-328X(98)01223-6

A general method for the synthesis of (CO)₄Fe[PPhX(C(O)R)] complexes from lithium acylferrates and PhXPCl is described (R = alkyl, phenyl, X = Ph, Cl). The X-ray crystal structure of (CO)₄Fe[PPh₂(C(O)Me)] has been determined and compared with that of other mononuclear acylphosphine complexes, which all possess a long P-C(O) bond. The weakness of this bond is revealed in nucleophilic and basic media, where (CO)₄Fe[PPh₂(C(O)R)] mostly leads to the [(CO)₄FePPh₂]^- anion. In the presence of LDA, however, some deprotonation occurs for R = Me, n-Bu, and subsequent addition of Ph₂PCl leads to monodentate α-phosphinoxyvinyl phosphine carbonyliron complexes in moderate yield.

Full text of DOI:10.1016/S0022-328X(98)01223-6

Journal of Organometallic Chemistry 579 (1999) 198–205
Synthesis and reactivity of acylphosphine tetracarbonyl–iron complexes
Jean-Jacques Brunet, Remi Chauvin *, Bruno Donnadieu, Erwan Thepaut
Laboratoire de Chimie de Coordination du CNRS,
UPR 8241 lie´e par con6entions a` l’Uni6ersite´ Paul Sabatier et a` l’Institut National Polytechnique, 205 route de Narbonne,
F-31077 Toulouse Cedex 4, France
Received 29 July 1998; received in revised form 3 December 1998
Abstract
A general method for the synthesis of (CO)4Fe[PPhX(C(O)R)] complexes from lithium acylferrates and PhXPCl is described
(R=alkyl, phenyl, X=Ph, Cl). The X-ray crystal structure of (CO)4Fe[PPh2(C(O)Me)] has been determined and compared with
that of other mononuclear acylphosphine complexes, which all possess a long P–C(O) bond. The weakness of this bond is
revealed in nucleophilic and basic media, where (CO)4Fe[PPh2(C(O)R)] mostly leads to the [(CO)4FePPh2]− anion. In the presence
of LDA, however, some deprotonation occurs for R=Me, n-Bu, and subsequent addition of Ph2PCl leads to monodentate
a-phosphinoxyvinyl phosphine carbonyliron complexes in moderate yield. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Acylphosphine; Acylchlorophosphine; (a-Phosphinoxyvinyl)phosphine; Tetracarbonyl–iron complex
1. Introduction
2. Results and discussion
Whereas phosphites ‘PO3’ [1], phosphines ‘PC3’ [2]
and phosphinites ‘PC2O’ [3] can be coordinated to the
iron atom of [HFe(CO)4]− by CO substitution (Scheme
1, reactivity I), the more basic and cumbersome
aminophosphines ‘PN3’ [4] or chloroaminophosphines
‘PClN2’ [5] bind to the iron atom of [HFe(CO)4]− by
H-substitution and concomitant hydrogenolysis of one
of the P–N or P–Cl bonds (Scheme 1, reactivity II) [6].
The reactivity II can be extended through the analogy
E=H[E=RC(O): novel acylphosphine complexes
have been prepared by tandem acylation-complexation
of a monochlorophosphine [7]. We now report on the
synthesis of new acylphosphine tetracarbonyl–iron
complexes, on their reactivity with nucleophiles (bind-
ing with the substrate) or bases (deprotonation of the
substrate and subsequent quenching with some elec-
trophile) and on a further extension of the study to a
dichlorophosphine substrate.
2.1. New acyldiphenylphosphine ironcarbonyl complexes
Most acylphosphine ligands known to date occur in
di- or trinuclear transition metal complexes [8], and
surprisingly, (diacyl)phosphine PR(C(O)R%)2 [9] and
carbonyl-diphosphines (PR2)2CO [10] have received
more attention than their simple models, (mono-
acyl)monophosphines. Whereas acylphosphine com-
plexes can be prepared from metallic precursors and
free acylphosphines [11], a one-pot procedure leads to
acylphosphine complexes from chlorodiphenylphos-
phine and lithium acylferrates (Scheme 2), prepared
from Fe(CO)5 and alkyllithium reagents [12]. Although
metallo–enolate resonance structures can be drawn
from acylferrate structures, no O-phosphinylation
products 2a–d are observed (Scheme 2): by contrast,
more electrophilic chlorophosphites have been recently
reported to react with acyltungstates at the oxygen end
[13].
An excess of ClPPh2 has been needed for a complete
conversion of the acylferrate reagent (IR monitoring):
* Corresponding author. Fax: +33-561553113.
E-mail address: chauvin@lcc-toulouse.fr (R. Chauvin)
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(98)01223-6

Journal of Organometallic Chemistry 579 (1999) 198–205
199
Scheme 1. Substitution reactivity of the hydridotetracarbonylferrate
anion (E=H) by various phosphanes (Y=X or C6H5). The reactiv-
ity path II is now studied for acyltetracarbonylferrate anions (E=
RC(O)).
in
a competitive process, ClPPh2 is reduced to
Ph2PPPh2 (the concomitant oxidation process of the
iron center, formally leading to ‘FeCl2’ derivatives, has
not been studied). The procedure for the synthesis of 3b
described in a preliminary communication [7] has been
optimized: only a one-and-one-tenth equivalent of
ClPPh2 is needed instead of the original two
equivalents.
In contrast, the selectivity in the benzoylphosphine
complex 3d is low, and four equivalents of ClPPh2 must
be used for a complete conversion of 1d. 3d could not
be isolated in a pure form (ca 60% selectivity with
respect to Ph2PPh2 based on the integrated 31P-NMR
spectrum), but was spectroscopically characterized in a
mixture with ClPPh2 and Ph2PPPh2.
Fig. 1. CAMERON view of the X-ray crystal structure of 3c. Molecular
strucrure of 3c showing the atom labelling scheme and thermal
ellipsoids at the 50% probability level. Hydrogen atoms are omitted
for clarity.
bond is already stretched in free acylphosphines: the
P–CꢀO l +PꢀC–O− resonance (pp conjugation) is
less important than the N–CꢀO l +NꢀC–O− reso-
nance in analogous amides [11a, 20], but is enhanced in
electron rich acylphosphines (e.g. in the h3-acylphos-
phide ClOs(CO)2(PPh3)2{P[C(O)t-Bu]H} with an 18
electron count at the osmium atom, the P–C(O) length
Whereas the n-Bu complex 3b is an oil (even at
−20°C), monocrystals of the new complex 3c deposited
from pentane and were subjected to X-ray diffraction
analysis. The structural features of 3c are similar to
those of the t-Bu complex 3a (Fig. 1, Table 2). A large
˚
is only 1.79 A [21]).
˚
P–C(O) bond length of ca 1.89 A is measured, which is
Regarding the reaction mechanism, the possibility of
a reductive elimination to RC(O)PPh2+Fe(CO)4 prior
to the formation of the acylphosphine complex 3a–3d
(Scheme 1) is ruled out by the absence of
(ClPh2P)Fe(CO)4 [22] and (Ph2PPh2P)Fe(CO)4 [25]
complexes which should result from a competitive trap-
ping of the 16-electron species Fe(CO)4 by the potential
ligands ClPPh2 or Ph2PPPh2 occurring in the reaction
medium.
greater than the sum of the covalent radii of P and C
˚
(rC+rP=1.83 A). Owing to the steric bulk of the
t-butyl substituent, an even longer P–C(O) bond of
˚
1.93 A was measured in 3a. This structural feature is a
common point of acylphosphine ligands in mononu-
clear carbonyl complexes (Table 3) [14–18] and of
carbonyldiphosphine ligands in dinuclear carbonyl iron
complexes [19]. Calculations showed that the P–C(O)
Scheme 2. One-step acylation-complexation of monochlorophosphines 3a–3d. The phosphinoxy Fischer carbene isomers 2a–2d were not observed.

200
J.-J. Brunet et al. / Journal of Organometallic Chemistry 579 (1999) 198–205
Table 1
Spectral data for complexes 3a–3d, 11b and 11c a
Complex (X, R)
NMR b
31P (s)
IR c
1
2
l
l
13C (PCO, d)
ꢀ JC(O)–Pꢀ (Hz)
l
13C (FeCO, d)
ꢀ JC(O)–Pꢀ (Hz)
w (PCꢀO) cm−1
3a (Ph, t-Bu) d
3b (Ph, n-Bu)
3c (Ph, Me)
3d (Ph, Ph)
11b (Cl, n-Bu)
11c (Cl, Me)
77.7
74.7
76.8
77.9
155.9
156.6
218.0
214.1
211.9
212.6
211.1 a
212.07
7.7
10.9
18.2
17.7
17
213.1
212.5
211.1
202.6
211.1 a
211.20
17.5
18.1
14.6
16.9
17
1678
1694
1697
1660
1704
1686
19.0
16.7
a The signals of (CO)4Fe and PCO are interpreted as superimposed.
b In CDCl3.
c In THF.
d See reference [7].
2.2.1. Reacti6ity of 3b with KOH
Complex 3b is inert in methanol (and in CD3OD),
but is cleaved upon addition of KOH: potassium pen-
tanoate 6 and complex 4 are the sole products identified
by NMR analysis. The presence of 4 is due to the
trapping of the intermediate phosphide anion
[(CO)4FePPh2]− by methanolic protons (Scheme 4: in
the presence of other electrophiles, other complexes
such as 7 or 9 should form: see Sections 2.2.2 and
2.2.3). Evaporation of methanol and extraction in THF
brings about a ligand redistribution between two
molecules of 4, and the final product is the trans-
(CO)3Fe(PHPh2)2 complex 5 (80% yield), which was
previously obtained by reaction of Fe(CO)5 with
NaBH4 in the presence of PHPh2 (Scheme 4) [23].
Scheme 3. Possible attacks of nucleophiles and bases (Z−) on
acylphosphine complexes.
2.2. Reacti6ity of acylphosphine carbonyliron complexes
with nucleophiles and bases
The acylation of ClPPh2 can be regarded as a car-
bonylation step in the synthesis of phosphine deriva-
tives, and might be followed by functionalization steps.
Three electrophilic reaction sites can be distinguished
(Scheme 3): the target of Z− could be either: (i) the C
atom of a carbonyl ligand (formation of an acylferrate
derivative, or in the case of Z=OH−, of a hydridofer-
rate after extrusion of CO2), (ii) the C atom of the acyl
group (with a subsequent cleavage of the P–C(O)
bond), or (iii) an acidic H atom at the a position of the
acyl group (formation of an enolate species which could
be subsequently C- or O-functionalized by
electrophiles).
2.2.2. Reacti6ity of 3b with NaBH4
The weakness of the P–C(O) bond prevents a simple
reduction of 3c into the a-hydroxyalkylphosphine com-
plex: complex 4 is isolated in 62% yield (non optimized)
from 3c and NaBH4 in methanol. Curiously, no ligand
redistribution to complex 5 is observed here upon ex-
traction in diethylether: the formation of 5 which was
mentionned in the preceeding section appears to be
specific to the presence of KOH.
Scheme 4. Reaction of 3b with nucleophiles or bases MB=KOH, NaBH4, n-BuLi, LDA.

J.-J. Brunet et al. / Journal of Organometallic Chemistry 579 (1999) 198–205
201
Table 2
Selected bond lengths (A) and bond angles (°) of complex 3c, as determined from X-ray diffraction data
˚
Bonds
Distances
Bonds
Distances
Bonds
Distances
Fe–P
2.2401(4)
1.791(2)
1.782(2)
1.824(2)
1.138(2)
1.806(2)
1.793(2)
1.894(2)
1.820(1)
O(3)–C(3)
O(5)–C(5)
C(6)–H(61)
C(6)–H(63)
C(11)–H(16)
O(2)–C(2)
1.146(2)
1.203(2)
0.81(3)
C(13)–C(14)
C(15)–C(16)
C(21)–C(26)
C(23)–C(24)
C(25)–C(26)
C(12)–C(13)
C(14)–C(15)
C(21)–C(22)
C(22)–C(23)
C(24)–C(25)
P–C(5)–O(5)
P–Fe–C(2)
1.381(3)
1.393(3)
1.392(2)
1.379(3)
1.386(2)
1.383(3)
1.374(3)
1.395(2)
1.392(2)
1.382(3)
118.7(1)
175.64(5)
86.36(5)
89.81(6)
Fe–C(2)
Fe–C(4)
P–C(11)
O(1)–C(1)
Fe–C(1)
Fe–C(3)
P–C(5)
0.88(3)
1.393(3)
1.138(2)
1.150(2)
1.485(3)
0.91(3)
1.387(3)
90.81(7)
110.70(6)
102.71(7)
102.24(7)
O(4)–C(4)
C(5)–C(6)
P–C(21)
C(6)–H(62)
C(11)–C(12)
C(2)–Fe–C(4)
Fe–P–C(5)
C(5)–P–C(11)
C(5)–P–C(21)
P–Fe–C(1)
91.28(5)
92.40(7)
121.37(8)
177.9(1)
C(1)–Fe–C(2)
C(1)–Fe–C(3)
Fe–C(2)–O(2)
P–Fe–C(3)
P–Fe–C(4)
Scheme 5. Synthesis of a-(diphenylphosphinoxy)vinyl diphenylphosphine iron tetracarbonyl complexes 10b and 10c.
reminiscent of their bidentate b-phosphinoxyvinyl-
2.2.3. Reacti6ity of 3b with n-BuLi
In an aprotic medium, the anion of 4, [(CO)4FePPh2]−
[24], can be generated by action of n-BuLi in THF, and
then trapped by an electrophile other than a proton.
Reaction of 3b with n-BuLi in THF followed by
treatment with Ph2PCl leads to the known complex 7
(l31P=3.22 (d), 62.0 (d) ppm, 1JPP=324 Hz [25]) which
is further characterized by 13C-NMR in CDCl3:
phosphine isomers [27].
2.3. Synthesis of acylchlorophosphine ironcarbonyl
complexes
Acylferrate 1b reacts with PhPCl2 to give the stable
acylchlorophosphine complex 11b in 79% yield. A similar
sequence leads from 1c to 11c, which could not be
completely purified, but which was spectroscopically
characterized (Scheme 6, Table 1).
2
l13C=128.44–135.57 and 213.07 ppm, dd, JPC=16
3
Hz, JPC=4.4 Hz.
Finally, attempts to apply the synthetic principle to the
reaction of lithium acylferrate 1b with PCl3 failed: the
final dark crude oil gave no NMR information
(paramagnetism).
2.2.4. Reacti6ity of 3b with LDA
While n-BuLi acts as a nucleophile, LDA has a more
basic character with respect to 3b, and the enolate 8b is
detected by IR spectroscopy. The enolate 8b reacts in situ
with CH3I and gives neither C- nor O-methylation
products, but the P-methylation product (CO)4Fe-
(PPh2Me) 9, with l31P= + 56.7 ppm [26]. By contrast,
enolates 8b and 8c react with Ph2PCl to give products
whose IR and NMR spectra are compatible with phos-
phinyl enol ethers 10b (30% crude yield) and 10c (42%
isolated yield) (Scheme 5).
3. Conclusions
This study paves the way to a broader use of
acylphosphines and acylchlorophosphines as direct
The reaction is not highly selective since Ph2PPPh2
derivatives resulting from a cleavage of the P–C(O) are
also observed in the NMR spectra of the crude reaction
medium. To the best of our knowledge, however, these
monodentate a-phosphinoxyvinyl phosphine ligands
with a novel structural sequence PIII–O–Csp2–P are
Scheme 6. Synthesis of acylchlorophosphine complexes by a tandem
acylation-complexation process.

202
Journal of Organometallic Chemistry 579 (1999) 198–205
reagents for the synthesis of phosphane transition
metal complexes. Owing to the weakness of the
FeP–C(O) bond, already indicated by X-ray
diffraction data, the chemistry of acylphosphine
tetracarbonyl–iron complexes in basic medium often
boils down to that of the [(CO)4FePPh2]− anion.
4.3. Preparations
4.3.1. Lithium acyltetracarbonylferrates 1b–d
A solution of of Fe(CO)5 (0.68 ml, 5 mmol) in 15
ml of THF was cooled to −78°C. A total of 3.1 ml
of a 1.6 M solution of RLi (5 mmol, R=n-Bu, Me,
Ph) were syringed in. The temperature was allowed to
rise to 20°C over a 2.5 h period. Completion of the
reaction was checked by IR analysis in the 1500–2500
cm−1 region and compared with data from the
literature [12].
Nonetheless
a
new type of a-phosphinoxyvinyl
phosphine complexes has been described, and their use
in selective bimetallic coordination chemistry can be
envisioned: the phosphinite end does not displace the
phosphine end at the iron center.
An extension of the strategy is underway, aimed at
the synthesis of formylphosphine complex 3e or its
phosphinoxy Fischer carbene isomer 2e (R=H, in
Scheme 2) from Na[(CO)4FeCHO] [28]. Efforts are
intended to elaborate a simple way to remove the
Fe(CO)4 moiety from the acylphosphine: this would
allow us for tackling a study of the steric and
electronic effects of acylphosphine ligands in transition
metal catalysis [10, 29].
1b R=n-Bu: wCO=2017 (m), 1927 (m), 1902–1895
(s), 1570 (m) cm−1
1c R=Me:
1d R=Ph:
wCO=2019 (m), 1929 (m), 1904–1896
(s), 1569 (m) cm−1
wCO=2020 (m), 1931 (m), 1912–1896
(s), 1596 (m) cm−1
4.3.2. Acyldiphenylphosphine tetracarbonyl–iron 3b–d
Ph2PCl (1.0 ml, 0.55 mmol for 3b, 1.8 ml, 10 mmol
for 3c, 3.6 ml, 20 mmol for 3d) was added to the
solution of the lithium acylferrates 1b–d (ca 5 mmol
in 15 ml of THF) at −78°C. After stirring for 12 h
between −78 and +20°C, the solvent was
evaporated, and the residue extracted in pentane
(3×15 ml).
4. Experimental
4.1. Materials
All experiments were performed under an argon
atmosphere using standard Schlenk techniques. THF
and diethylether were distilled over Na/benzophenone
be-fore use. Commercial synthesis grade pentane and
methanol were degassed by bubbling argon before use.
Potassium hydroxide (Technical 86%, Prolabo),
pentacarbonyliron (Fluka), n-butyllithium (1.6 M in
After evaporation of pentane, spectroscopically pure
3b was obtained as a brown oil (1.90 g, 87%). IR
(THF): w=2051 (m), 1977 (m), 1947 (s), 1694 (w)
1
cm−1. H-NMR (CDCl3): l=0.87 (t, 2 H, CH3CH2);
1.30 (m,
2
H, CH3CH2CH2); 1.65 (m,
2
H,
CH2CH2CH2); 2.83 (t, 2 H, CH2CH2CO); 7.41–7.68
(10 H, aromatic CH). 31P-NMR (CDCl3): l=74.8
(Ph2P). 13C-NMR (CDCl3): l=13.73 (s, CH3); 21.98
(s, CH3CH2CH2); 25.98 (s, CH2CH2CH2); 42.47 (d,
hexane,
Aldrich),
phenyllithium
(1.6
M
in
cyclohexane/ether, Aldrich), methyllithium (1.6 M in
diethylether, Fluka), and lithium diisopropylamide
(LDA, 2 M in THF/heptane/ethylbenzene, Aldrich)
were used without further purification. Ph2PCl
(Aldrich) and PhPCl2 (Aldrich) were distilled before
use.
2
CH2CH2CO, JPC=41.7 Hz); 128.93–133.68 (aromatic
C); 212.45 (d, Fe(CO)4, 2JPC=18.1 Hz); 214.10 (d,
1
PCO, JPC=10.9 Hz).
Crystallization from pentane afforded 3c as a yellow
solid (1.08 g, 55%). M.p.=89–91°C. Microanalysis:
C18H13O5PFe (396.12): Anal. Calc. C 54.58, H 3.31;
Found C 55.82, H 3.36. IR (THF): w=2052 (m), 1978
4.2. Measurements
IR spectra were recorded in the 1500–2500 cm−1
region on a Perkin–Elmer 1725X FT-IR spectrometer
using CaF2 windows. NMR spectra were recorded on
(m), 1945 (s), 1697 (w) cm−1 1H-NMR (CDCl3):
.
l=2.46 (d, 3 H, CH3, 3JPH=4.5 Hz); 7.40–7.65
(10H, aromatic CH). 31P-NMR (CDCl3): l=76.8
(Ph2P). 13C-NMR (CDCl3): l=29.69 (d, CH3,
2JPC=46.5 Hz); 128.18–133.27 (aromatic C); 211.09
(d, Fe(CO)4, 2JPC=14.6 Hz); 211.93 (d, PCO,
1JPC=18.2 Hz).
1
a Brucker AC 200 spectrometer: at 200 MHz for H,
81 MHz for 31P and 50 MHz for 13C, with positive
chemical shifts at low field expressed in ppm by
internal reference to TMS for 1H and 13C and by
external reference to 85% H3PO4 in D2O for 31P.
X-ray diffraction experiments were carried out on a
STOE IPDS (imaging plate diffraction system)
equipped with an Oxford cryosystem cooler device
After evaporation of pentane, 3d was obtained as a
mixture with Ph2PPPh2 (60% 3d, 40% Ph2PPh2) and
excess ClPPh2. IR (THF): w=2051 (m), 1977 (m),
1948 (s), 1660 (w) cm−1
.
1H-NMR (CDCl3):
l=7.37–7.83 (15 H, aromatic CH). 31P-NMR
˚
using Mo–Ka radiation (u=0.71073 A).

J.-J. Brunet et al. / Journal of Organometallic Chemistry 579 (1999) 198–205
203
(CDCl3): l=77.9 (s, Ph2P) ppm. 13C-NMR (CDCl3):
l=126.79–138.79 (aromatic C), 202.60 (d, Fe(CO)4,
dryness, giving 5 as an oil (0.180 g, 80%=traces of 4).
IR (THF): w=2016 (w), 1896 (s) cm−1 31P-NMR
.
2JPC=16.9 Hz), 212.60 (d, PCO, JPC=17.7 Hz).
(CDCl3): l=53.7 (d, 1JPH=365.3 Hz). 13C-NMR
(CDCl3): l=128.82–132.66 (aromatic C); 212.69 (t,
1
2
4.3.3. Acylchlorodiphenylphosphine tetracarbonyl–iron
11b
CO, JPC=30 Hz). The insoluble solid was identified as
1
pure potassium pentanoate 6: H-NMR (CD3OD): l=
PhPCl2 (0.68 ml, 5 mmol) was added to a solution of
the lithium acylferrate 1b (ca 5 mmol) in THF (15 ml)
at −78°C. After stirring for 12 h between −78 and
+20°C, the solvent was evaporated. The residue was
extracted in pentane (3×15 ml) and the solvent evapo-
rated to dryness to give 11b as a brown oil (1.57 g,
79%). IR (THF): w=2064 (m), 1999 (m), 1969 (s), 1704
1.01 (t, 3 H,CH3CH2); 1.44 (m, 2 H, CH3CH2CH2);
1.67 (m,
2
H, CH2CH2CH2); 2.49 (t,
2
H,
CH2CH2COO−). 13C-NMR (CD3OD): l=14.64
(CH3CH2); 24.18 (CH3CH2CH2); 30.36 (CH2CH2CH2);
39.43 (CH2CH2COO−); 183.55 (COO−).
4.3.6. h-Phosphinoxy6inyl phosphine tetracarbonyl–iron
complxes 10c and 10b
.
(w) cm−1 1H-NMR (CDCl3): l=0.87 (t, 3 H,
CH3CH2); 1.30 (m, 2 H, CH3CH2CH2); 1.64 (m, 2 H,
A solution of 2 M LDA (0.70 ml 1.4 mmol) was
synringed into a solution of 3c (1.0 mmol) in THF (10
ml) at −78°C. The solution was stirred for 45 min
between −78 and −50°C: the enolate 8c was detected
by IR in THF (w=2036, 1933, 1593 cm−1). The solu-
tion was cooled back to −78°C, and ClPPh2 (0.25 ml,
1.4 mmol) was added. After stirring overnight between
−78 and 20°C, the solution was filtered and evapo-
rated to dryness. The oily residue was extracted in
pentane (2×10 ml), and the solution was kept at
−15°C until an oil deposited. The supernatant was
separated and evaporated to give the O-phosphinyla-
tion product 10c Scheme 5 (0.363 g, 42%): IR (THF):
2
3
CH2CH2CH2); 2.88 (m, 1 H, JHH=18.2 Hz, JPH=2
Hz) and 2.97 (m,
H, 2JHH=18.1 Hz): (2
1
diastereotopic H in CH2CH2CO) 7.79–7.86 (5 H, aro-
matic CH). 31P-NMR (CDCl3): l=155.9 (PhPCl). 13C-
NMR (CDCl3): l=13.64 (s, CH3CH2); 21.92 (s,
CH3CH2); 25.81 (s, CH2CH2CH2); 39.92 (d,
2
CH2CH2CO, JPC=46.9 Hz); 127.38–133.02 (aromatic
2
1
C); 211.11 (2 d, Fe(CO)4 and PCO, JPC ca JPC ca 17
Hz).
A similar procedure leads from 1c to 11c (sensitive
compound which could not be purified on silica gel
column, but which was spectroscopically identified). IR
(THF): w=2057 (m), 1988 (m), 1951(s), 1686 (w) cm−1
.
w=2049 (m), 1981 (m), 1948 (s), 1598 (w) cm−1. H-
1
3
1H-NMR (CDCl3): l=2.58 (d, 3 H, CH3CO, JPH
=
NMR (CDCl3): l=4.99 (ddd,2JHH=3.4 Hz, 3JPH=9.6
4.8 Hz); 7.47–7.59 (5 H, aromatic CH). 31P-NMR
(CDCl3): l=156.6 (PhPCl). 13C-NMR (CDCl3): l=
129.31–137.20 (aromatic C); 211.20 (d, Fe(CO)4,
Hz, 4JPH=2.5 Hz); 5.50 (ddd,2JHH=3.4 Hz, JPH
=
3
30.0 Hz, JPH=3.2 Hz); 7.25–7.50 (aromatic H). 31P-
NMR (CDCl3): l=76.2 (s, (CO)4Fe-PPh2-C); 114.9 (s,
O-PPh2). 13C-NMR (CDCl3): l=108.14 (dd, =CH2,
4
1
2JPC=16.7 Hz); 212.07 (d, PCO, JPC=19.0 Hz).
2JCP ca JCP ca 17 Hz); 128.59–134.33 (aromatic C);
3
2
1
4.3.4. (CO)4Fe(PHPh2) 4
157.26 (dd, PPh2-C(O-PPh2), JCPB5 Hz, JCP=63.9
2
A sample of 0.053 g (1.5 mmol) of NaBH4 was added
to a solution of 0.200 g (0.5 mmol) of 3c in 10 ml of
methanol at 0°C. After stirring for 20 min at 0°C and
then 30 min at 20°C, the solvent was evaporated. The
residue was treated with 10 ml of water and 10 ml of
diethylether under stirring. The organic layer was sepa-
rated, dried over MgSO4, filtered and evaporated to
dryness to give 4 (0.110 g, 62%). IR (THF): w=2053
Hz); 213.39 (d, (CO)4Fe, JCP=19.5 Hz).
A similar procedure leads from 3b to 8b (IR (THF):
w=2037, 1940, 1588 cm−1) and 10b Scheme 5 (30%
crude yield). IR (THF): w=2052 (m), 1979 (m), 1943
Table 3
Crystal data of mononuclear (monoacyl)phosphine carbonyl com-
plexes
1
(w), 1972 (m), 1943 (s) cm−1. H-NMR (CDCl3): l=
1
6.95 (d, 1 H, PH, JPH=374 Hz); 7.60–7.66 (aromatic
˚
1
CH). 31P-NMR (CDCl3): l=42.7 (d, PH, JPH=377
Complexes
P–C(O) (A) Ref.
Hz). 13C-NMR (CDCl3): l=129.12–132.77 (aromatic
3a
3b
1.93
1.89
[7]
2
C); 212.77 (d, CO, JPC=20.2 Hz).
This
work
[14]
[15]
[16]
[17]
4.3.5. trans-(CO)3Fe(PHPh2)2 5
BrMn(CO)4{P[C(O)CCl3]PhMe}
BrMn(CO)4{P[C(O)CH2CHMeCl]Ph2}
AcMoCp(CO)2{P[COMe]Ph2}
IWCp(CO){P[C(O)CH2p-tol][o-PH2C6H4]
[(CH2)4I]}
1.90
1.89
1.89
1.90
A solution of KOH (0.111 g, 1.7 mmol) in methanol
(8 ml) was pourred into a solution of 3b (0.373 g, 0.85
mmol) in methanol (2 ml) at 0°C. After 0.5 h, the
temperature rose to 20°C and the solvent was evapo-
rated. The green-brown residue was extracted in THF
(2×20 ml): the solution was filtered and evaporated to
IWCp(CO){P[C(O)CH2p-tol][o-PH2C6H4]Me} 1.91
W(CO)5{P[C(O)PhCꢀCPh]PhMe} 1.93
[17]
[18]

204
Journal of Organometallic Chemistry 579 (1999) 198–205
1
(s), 1587 (w) cm−1. H-NMR (CDCl3): l=0.71 (t, 3
H, CH3); 1,28 (m, 2 H, CH3CH2); 2.09 (m, 2 H,
CH3CH2CH2); 6.11 (m, 1 H, CH, 3JPH=11.4 Hz,
4JPHB2 Hz); 7.23–7.35 (aromatic H). 31P-NMR
(CDCl3): l=76.8 (s, (CO)4Fe-PPh2-C); 122.9 (s, O-
PPh2). 13C-NMR (CDCl3): l=13.50 (q, CH3-CH2,
1JCH=125 Hz); 22.60 (t, CH3CH2CH2, 1JCH=126
Hz); 29.65 (t, CH3CH2CH2, 1JCH=126 Hz); 149.10
5. Supplementary material
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 115134 for 3c. Copies of the
information can be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge, CB2
1EZ, UK (Fax: +44-1223-336-033; e-mail: de-
posit@ccdc.cam.ac.uk or www: http://www.ccdc.
cam.ac.uk). Details of the X-ray structure deter-
mination of complex 3c are also available from the
author.
2
1
(dd, PPh2-C(O-PPh2), JCP=5.2 Hz, JCP=59.9 Hz);
128.02–133.25 (ꢀCH and aromatic C); 213.21 (d,
(CO)4Fe, JCP=18.8 Hz).
2
4.4. Experimental data for the X-ray crystal structure
determination of 3c
Acknowledgements
Crystal data for C18H13O5PFe: M=396.12, triclinic
crystal of dimensions: 0.50×0.40×0.30 mm3 (space
This work was supported by the Centre National de
la Recherche Scientifique. The authors wish to thank
Ms L. Noe´ for performing microanalyses.
˚
(
group P1 with unit cell a=8.872(1) A, b=8.6078(1)
˚
˚
A, c=12.606(2) A, h=84.20(2)°, i=83.19(2)°, k=
69.23(2)°, V=892 (2) A , Z=2, zcalc. =1.47 g cm−3
,
3
˚
v=9.55 cm−1, F(000)=404.88. A total of 6863
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