Reactivity of metallophosphide anions with electrophilic (arene)tricarbonylmetal complexes

Article abstract of DOI:10.1002/ejic.200200531

Reaction of metallophosphide anions [(CO)_xM′PPh₂]- (M′ = Cr, Fe) with neutral tricarbonyl(η⁶-fluoroarene) chromium and cationic (η⁶-arene)tricarbonylmanganese complexes give rise to the formation of dinuclear co

Full text of DOI:10.1002/ejic.200200531

FULL PAPER
Reactivity of Metallophosphide Anions with Electrophilic
(Arene)tricarbonylmetal Complexes
Virginie Comte,[a] Jean Philippe Tranchier,[b] Francoise Rose-Munch,*[b] Eric Rose,[b]
¸
[a]
[a]
[a]
`
¨
Daniele Perrey, Philippe Richard, and Claude Moıse
Keywords: Anions / Carbonyl ligands / Arene ligands / Manganese / Chromium / Iron
Reaction of metallophosphide anions [(CO)xMЈPPh2]− (MЈ =
Cr, Fe) with neutral tricarbonyl(η6-fluoroarene)chromium
and cationic (η6-arene)tricarbonylmanganese complexes
give rise to the formation of dinuclear complexes. These
complexes are obtained either by substitution of the fluoride
anion in the (arene)chromium complexes, or by addition to
the ring in the (arene)manganese complexes. The X-ray
structure of one homodimetallic (Cr−Cr) complex was ob-
tained and compared with its solution structure.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
ties].[8] Metal insertion into the CϪCl bond of cationic
tricarbonyl(chloroarene)manganese complexes was also
seen.[9a]
Arenes coordinated to electrophilic neutral Cr(CO)3 or
cationic Mn(CO)3 groups undergo a large variety of trans-
formations that would otherwise not be feasible with the
free arenes.[1] Among them, nucleophilic additions, followed
by acidic and (or) oxidative treatment, provide efficient ac-
cess to functionalized arenes or cyclohexadienes.[1,2] A wide
range of carbon nucleophiles have been shown to react with
(η6-arene)tricarbonylchromium and -manganese com-
plexes,[1] but relatively few investigations have been carried
out using organometallic derivatives as the nucleophiles.
In the Mn series, benzylic and homobenzylic organomet-
allic carbanions have been used as nucleophiles. Beck et al.,
for example, described the reactivity of Mn complexes with
deprotonated diphenylmethane or benzothiophene coordi-
nated to Cr(CO)3,[3] as well as with carbonylosmate,[4] car-
bonylrhenate[5] and anionic alkynyl complexes.[6] More re-
cently, Sweigart et al.[7] demonstrated that a weak nucleoph-
ile such as [Pt(PPh3)2(C2H4)] could cleave a strained CϪC
bond in the four-membered ring of biphenylene coordi-
nated to an Mn(CO)3ϩ fragment, giving the insertion prod-
uct. Similarly, metal insertion into the CϪS and CϪO
bonds of benzothiophene and benzofuran, respectively, was
also observed [the carbocyclic rings of the benzothiophene
Our own contribution in this field has been aimed at
studying the reactivity of Fischer-type carbene anions[10]
and of deprotonated (alkoxy-substituted arene)tricarbon-
ylchromium complexes[11] towards (η6-arene)tricarbonyl-
manganese complexes. These reactions result in the forma-
tion of heterodi- or -polymetallic complexes.
In the Cr series, strongly nucleophilic organometallic
anions [such as Fe(CO)42Ϫ, M(CO)52Ϫ, M ϭ Cr, W,
CpFe(CO)2Ϫ] reacted with [(C6H5X)Cr(CO)3], allowing the
formation of dinuclear complexes, which arise as a result of
halogen substitution by the organometallic anions.[12]
This has led us to investigate the reaction of metallophos-
phide anions with (η6-arene)metal complexes, and for this
purpose we have selected the [(CO)xMЈPPh2]Ϫ anions.
These metallophosphide anions are, for example, able to
achieve Cp substitution in neutral molybdenocene and
tungstenocene dichlorides.[13] The presence of tert-butyl or
trimethylsilyl groups on the cyclopentadienyl rings does not
affect the site of substitution, and products with 1,3-disub-
stituted Cp-ring[13d] (Scheme 1) are obtained.
ϩ
and the benzofuran were coordinated to Mn(CO)3 enti-
[a]
`
`
d’Electrosynthese
Laboratoire
de
Synthese
et
´
´
Organometalliques, UMR CNRS 5632, Faculte des Sciences
Gabriel,
21000 Dijon, France
[b]
`
´
Laboratoire de Synthese Organique et Organometallique, UMR
CNRS 7611, Universite Pierre et Marie Curie, Tour 44 Ϫ 1er
´
´
etage,
4, Place Jussieu, 75252 Paris Cedex 05, France
rosemun@ccr.jussieu.fr
Scheme 1. Reaction of metallophosphide anions with metallocene
dichlorides
Eur. J. Inorg. Chem. 2003, 1893Ϫ1899
DOI: 10.1002/ejic.200200531
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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V. Comte, J. P. Tranchier, F. Rose-Munch, E. Rose, D. P. P. Richard, C. Mo¨ıse
FULL PAPER
Scheme 2. Reaction of metallophosphide anions with (η6-arene)Mn(CO)3 complexes
ϩ
Reactivity towards [(η6-Arene)Mn(CO)3]؉ Complexes
This unexpected reactivity led us to believe that metallo-
phosphide anions are rather good nucleophiles.
In this paper, we describe the reactivity of two metallo-
phosphide anions towards several substituted (η6-arene)m-
anganese and -chromium complexes (complexes 1,
Scheme 2; and 4, Scheme 3). The conformational study of
one of the resulting dinuclear complexes in the solid state
and in solution is also presented.
In a preliminary experiment, treatment of a suspension
of [(η6-C6H6)Mn(CO)3](PF6) (1a) in THF with PPh2Li[16]
at Ϫ80 °C resulted in the formation of the addition product,
the η5-cyclohexadienyl complex 2a[17] in a 40% yield, ac-
cording to Scheme 2.
It is worth noting that when PPh2Li was added to bent
metallocenes [(η5-C5H5)2MCl2] (M ϭ Mo, W), the com-
plexity of the reaction mixture did not permit isolation of
the desired product.[18a] Similarly, treatment of complex 1a
with [(CO)xMЈPPh2]Li afforded the neutral complexes
3a[Cr] and 3a[Fe] in 55 and 35% yields, respectively. If the
reaction was performed with anisole and the 1,3-dimeth-
oxybenzene complexes, 1b and 1c, dimetallic derivatives
3b[Cr], 3b[Fe] and 3c[Cr][18b] were recovered in 55, 55 and
65% yields, respectively (Scheme 2). It is important to em-
phasize the meta regioselectivity[19] of the nucleophilic ad-
dition with respect to the methoxy group in the cases of 1b
and 1c.
1
The H NMR spectra of the resulting neutral addition
Scheme 3. Reaction of metallophosphide anions with (η6-arene)-
Cr(CO)3 complexes
complexes (Table 1) features the characteristic signals for
the η5-cyclohexadienyl groups, the 1-H and 5-H protons
display low-frequency resonances (between δ ϭ 3.00 and
3.57 ppm), the 2-H and 4-H protons show resonances at
almost the same frequency (δ ϭ 4.85Ϫ5.07 ppm), and the
Results and Discussion
The starting (arene)tricarbonylmanganese (1aϪc) and - 3-H protons give signals at the highest frequency (δ ϭ
chromium (4aϪc) complexes were prepared according to 5.04Ϫ5.47 ppm) for the dinuclear complexes 3a[Cr], 3a[Fe],
literature procedures.[14,15]
3b[Cr], 3b[Fe], and 3c[Cr] (Entries 2Ϫ6, Table 1), and at
1
Table 1. H NMR spectroscopic data of 6-substituted tricarbonyl[(η5-1,2,3,4,5)-cyclohexadienyl]manganese complexes
Entry
Complex[a]
1-H, 5-H
2,4-H
3-H
6-H
Ph
1
2
3
4
5
6
2a
3.16[b] (dd)
5.04[b] (dd)
4.85[b] (dd)
4.99[b] (dd)
4.90[b] (dd)
5.07[b] (dd)
Ϫ
6.06[b] (t)
5.18[b] (t)
5.47[b] (t)
5.11[b] (d)
5.42[b] (d)
5.04[f] (t)
3.73 (m)
4.30[c] (td)
4.36 (m)
4.39 (m)
4.47 (m)
4.38[g] (dt)
7.36 (m)
7.54 (m)
7.59 (m)
7.55 (m)
7.55 (m)
7.55 (m)
3a[Cr]
3a[Fe]
3b[Cr][d]
3b[Fe][d]
3c[Cr][e]
3.56[b] (dd)
3.57[b] (dd)
3.39[d] (m), 3.56[b] (dd)
3.00(m), 3.56[b] (dd)
3.00 (m), 3.56[b] (dd), 3.40 (m)
[a]
[b] 3
[c] 3
2
[d]
[e]
CD3COCD3, multiplicity is given in parentheses.
J
H,H
ϭ 5.9 Hz.
J
H,H
ϭ JHP ϭ 5.9 Hz. OMe: δ ϭ 3.39. OMe: δ ϭ 3.44.
[f] 4
[g] 2
3
J
H,H
ϭ 2 Hz.
J
HP
ϭ 9.3 Hz; JH,H ϭ 5.6 Hz.
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Reactivity of Metallophosphides with (Arene)tricarbonylmetal Complexes
FULL PAPER
even higher frequency (δ ϭ 6.06 ppm) for the mononuclear due, display signals at the highest frequency (between δ ϭ
complex 2a (Entry 1, Table 1).
5.80 and 6.12 ppm; Entries 1, 2, 4Ϫ6, Table 2).
The resonance for 6-H in the mononuclear complex 2a
presents a signal at δ ϭ 3.73 ppm, in agreement with that
previously observed for the product obtained after addition
of phosphate to coordinated [(arene)Mn(CO)3]ϩ cat-
ions.[19c] The signals for the 6-H protons of the dinuclear
complexes (Entries 2Ϫ6), which can be used as a probe for
the coordination of PPh2 to the MЈ(CO)x entity, display a
high-frequency shift, δ ϭ 4.30Ϫ4.47 ppm. This is consistent
with the coordination of a phosphorus atom to a metal
center.
This is in agreement with an anti-eclipsed conformation
of the tripod, with respect to the bulky phosphanyl
group.[1g] Similarly, the eclipsed 2-H and 6-H protons pre-
sent signals at a high frequency. The biggest difference in
the chemical shifts observed for two adjacent protons (3-H
and 4-H) is δ ϭ 0.92 ppm for complex 5b. This is due to
the synergic effect of the electron-donating methyl group,
which favors an eclipsed conformation, and the phosphanyl
group, whose steric hindrance favors an anti-eclipsed con-
formation. This confirms that the main conformation of the
tripod in solution is eclipsed, with respect to the methyl
group.[1d]
Reactivity Towards (η6-Arene)Cr(CO)3 Complexes
The IR spectra of Cr(CO)3 present two well-resolved
stretching modes, in accordance with the C3v symmetry.[22]
The absorptions are assigned to a nondegenerate symmetry
vibration A1, and a doubly degenerate asymmetric vi-
bration E.[22]
In order to evaluate the effect of complexation of the
phosphorus atom by the MЈ(CO)x metal fragment, we com-
pared some selected IR and 1H NMR spectroscopic data of
the mononuclear and dinuclear complexes of this chromium
series (Table 3).
In all cases, a shift to higher wavenumbers is observed
for the carbonyl stretching vibrations of the Cr(CO)3 entity
for the dimetallic complexes. This is in agreement with a
stronger CO force constant, and with a decrease in the re-
tro-donation of the chromium towards the carbonyl groups.
In the NMR spectra, the 6-H protons (β to the phosphorus
atom) of the dinuclear complexes present signals at a much
higher frequency than those of the mononuclear complexes,
e.g. the ∆δ(6-H) [δ(6-Hdinuclear) Ϫ δ(6-Hmononuclear)] could
reach δ ϭ 0.57 ppm for 6c[Fe] (Entry 8, Table 3).
The tricarbonyl(η6-haloarene)chromium complexes 4a,
4b and 4c reacted with PPh2Li in THF in the presence of
freshly distilled HMPT; derivatives 5a,[20] 5b and 5c, respec-
tively, were obtained in 60% yields (Scheme 3).
No reaction takes place in the absence of HMPT (which
increases the nucleophilicity of the anions), emphasizing the
low electrophilic nature of the Cr complexes. The easy for-
mation of 5b shows that steric effects, due to the presence
of the ortho-methyl group, play no part. These metallophos-
phane complexes could lead to many µ-phosphido-bridged
heteropolymetallic complexes. For example, we were able to
synthesize such a dimetallic system incorporating a group-
8 metallocene derivative.[21]
Similarly, by using [(CO)xMЈPPh2]Li (x ϭ 5, MЈ ϭ Cr
and x ϭ 4, MЈ ϭ Fe), dimetallic complexes 6a[Cr], 6b[Cr],
6b[Fe][18b] (Scheme 3) were isolated in 85, 80 and 60% yields,
1
respectively. Their H NMR spectroscopic data (Entries 1,
2, 4Ϫ6, Table 2) are consistent with ipso-nucleophilic aro-
matic substitution occurring at the carbon atom bearing the
fluoride atom. The same regioselectivity was clearly ob-
served when using the para-disubstituted complex 4c as the
starting material. This afforded the new para-disubstituted
complexes 5c, 6c[Cr] and 6c[Fe] (Scheme 3). No cine- or
tele-SNAr was observed.[1d]
In order to know more about the conformation of these
complexes in the solid state, an X-ray analysis was per-
formed on crystals of complex 6b[Cr]. Two views of the
ORTEP diagram are presented in Figure 1.
It is important to note the influence of the PPh2 or the
First of all, the two metallic moieties lie on both sides
PPh2MЈ(CO)x unit on the conformation of the Cr(CO)3 tri- of the arene ring. The Cr(CO)3 moiety adopts an eclipsed
pod. Indeed the 4-H protons, para to the phosphanyl resi- conformation relative to the methyl group. It is worth not-
1
Table 2. H NMR spectroscopic data of tricarbonyl[η6-(1-substituted arene)]chromium complexes
Entry
Complex[a]
2-H
3-H
4-H
5-H
6-H
Ph
1
2
3
4
5
6
7
8
5a
5.56[b] (dd)
Ϫ
5.45 (m)
5.86[b] (dd)
Ϫ
5.40[c] (dd)
4.91 (m)
5.45 (m)
5.50[c] (dd)
5.41 (m)
5.37 (m)
5.44[j] (d)
5.54[j] (d)
5.80[c] (t)
5.83[c] (dd)
Ϫ
6.06[c] (t)
6.10[c] (dd)
6.12 (m)
Ϫ
5.40[c] (dd)
5.50 (m)
5.45 (m)
5.50[c](dd)
5.45 (m)
5.37 (m)
5.44[j] (d)
5.80[j] (d)
5.56[b] (dd)
5.36[b] (dd)
5.45 (m)
7.50 (m)
7.50 (m)
7.55 (m)
7.75 (m)
7.70 (m)
7.70 (m)
7.55 (m)
7.60 (m)
5b[d]
5c[e]
6a[Cr]
6b[Cr][f]
6b[Fe][g]
6c[Cr][h]
6c[Fe][k]
5.86[b] (dd)
5.63[b] (dd)
5.45 (m)
Ϫ
5.90[i] (dd)
6.02[j] (dd)
5.90[i] (dd)
5.98[i] (dd)
Ϫ
[a]
CD3COCD3, multiplicity is given in parentheses. [b] 3JH,H ϭ 3JPH ϭ 5.9 Hz. [c] 3JH,Hϭ5.9 Hz. [d] Me: δ ϭ 2.26. [e] Me: δ ϭ 2.23. [f] Me:
[g]
[h]
[i] 3
3
[j] 3
[k]
δ ϭ2.11. Me: δ ϭ 2.16. Me: δ ϭ 2.33.
J
H,H
ϭ JPH ϭ 6.4 Hz.
J
H,H
ϭ 6.4 Hz. Me: δ ϭ 2.35.
Eur. J. Inorg. Chem. 2003, 1893Ϫ1899
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V. Comte, J. P. Tranchier, F. Rose-Munch, E. Rose, D. P. P. Richard, C. Mo¨ıse
Table 3. Selected IR and H NMR spectroscopic data for (arene)chromium complexes
FULL PAPER
1
Entry[a][b]
Complex
ν(CrϪCO), A1 mode
ν(CrϪCO), E mode
∆νA1, ∆νE
δ(6-H)
∆δ(6-H)
ϩ0.30
1
2
3
4
5
6
7
8
5a
6a[Cr]
5b
6b[Cr]
6b[Fe]
5c
6c[Cr]
6c[Fe]
1969
1978
1971
1972
1972
1970
1973
1976
1899
1909
1895
1898
1897
1900
1901
1901
5.56
5.86
ϩ9[c], ϩ6[c]
ϩ1[d], ϩ3[d]
ϩ1[e], ϩ2[c]
5.45
5.90
6.02
ϩ3[f], ϩ1[f]
ϩ6[g], ϩ1[g]
ϩ0.45
ϩ0.57
[a]
[b]
[c]
[d]
[e]
IR spectra in THF [cmϪ1]. NMR spectra in CDCl3 [ppm]. ∆ν ϭ ν6a[Cr] Ϫ ν5a. ∆ν ϭ ν6b[Cr] Ϫ ν5b. ∆ν ϭ ν6b[Fe] Ϫ ν5b.
[f]
[g]
∆ν ϭ ν6c[Cr] Ϫ ν5c. ∆ν ϭ ν6c[Fe] Ϫ ν5c.
˚
phorus atom, whose C1ϪP bond length is 1.843(2) A, dis-
˚
plays a shift of 0.471(2) A out of the mean-aromatic plane,
away from the Cr center.[23] The metal-to-ring distance is
˚
1.724(2) A. It is interesting to compare this structure with
the tricarbonyl[(diisopropylphosphanyl)benzene]chromium
structure (complex A), which presents a partially eclipsed
conformation of the Cr(CO)3 entity (midway between
eclipsed and staggered, relative to the η6-phenyl ring).[20a]
In Table 4, selected bond lengths of complexes A and 6b[Cr]
are reported for comparison; coordination of the phos-
phorus substituent to Cr(CO)5 does not seem to signifi-
cantly affect these values. However, a small increase in the
CrϪC1 bond length is induced.
[20a]
˚
Table 4. Selected bond lengths [A] of complexes A
and 6b[Cr]
Conclusion
Figure 1. Two views of the ORTEP diagram of 6b[Cr]; thermal
ellipsoids are drawn at the 50% probability level; selected param-
eters: CNTϪCr1 1.724(2), C1ϪP 1.843(2), Cr2ϪP 2.4107(5),
C1ϪPϪCr2 108.19(6)
Metallophosphide anions readily react with electrophilic
(η6-arene)tricarbonylmanganese (by nucleophilic additions)
and chromium complexes (by ipso-nucleophilic substi-
tutions), and allow the easy formation of neutral dinuclear
ing that the longest chromiumϪcarbon bond length is seen complexes, one of which has been fully characterized by X-
˚
for CrϪC1 [2.268(2) A], for the carbon atom substituted by ray analysis. Both types of reactions are useful in the syn-
the phosphane group, whereas the chromiumϪcarbon bond thesis of highly functionalized arylphosphane complexes,
length CrϪC2, for the carbon atom substituted by the and they might therefore complement the methods pre-
˚
methyl group, is 2.255(2) A. The four other bond lengths viously described where nucleophilic arene derivatives are
˚
are in the range 2.204Ϫ2.222 A. Furthermore, the phos- treated with electrophilic phosphanes XPR2.
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Reactivity of Metallophosphides with (Arene)tricarbonylmetal Complexes
FULL PAPER
(CD3COCD3): δ ϭ 3.39 (s, 3 H, OMe) ppm; see Table 1. 31P{1H}
NMR (CD3COCD3): δ ϭ 77.3 (s) ppm.
Experimental Section
General Comments: All reactions were carried out under purified
argon. The solvents and eluents were dried by an appropriate pro-
cedure and distilled under argon from sodium and benzophenone
immediately before use. Standard Schlenk techniques and conven-
tional glass vessels were employed. Column chromatography was
performed under argon with silica gel (70Ϫ230 mesh). Elemental
analyses were carried out with an EA 1108 CHNS-O FISONS In-
struments. 1H (200 MHz), 31P (81 MHz) and 13C (50 MHz) spectra
were collected with a Bruker AC 200 spectrometer. Chemical shifts
are relative to internal TMS (1H, 13C) or external H3PO4 (31P). IR
spectra were recorded with a Nicolet 205 IR-FT. The lithium re-
agent [(CO)xMЈPPh2]Li (x ϭ 5, MЈ ϭ Cr; x ϭ 4, MЈ ϭ Fe) was
prepared according to a literature method,[24] using low-chloride
methyllithium (Janssen). The manganese complexes were prepared
according to two different procedures, using [BrMn(CO)5] with
AlCl3 or AgBF4 and the free arenes.[14] The syntheses of the chro-
mium complexes were achieved by heating [Cr(CO)6] and the free
arene in a 9:1 mixture of di-n-butyl ether and THF.[15]
[(η5-C6H4-1-OMe-3-OMe-5-R3)Mn(CO)3] {R3 ؍ PPh2Cr(CO)5:
3c[Cr]}: Yellow crystalline powder (425 mg, 65% yield). IR (νCO,
1
THF): ν˜ ϭ 2061 (m), 2018 (s), 1983 (w), 1937 (s) cmϪ1. H NMR
(CD3COCD3): δ ϭ 3.44 (s ϩ m, 8 H, OMe, 1-H ϩ 5-H) ppm; see
Table 1. 31P{1H} NMR (CD3COCD3):
δ ϭ 61.3 (s) ppm.
C28H20CrMnO10P (654.4): calcd. C 51.39, H 3.08; found C 52.17,
H 3.79.
(Arene)chromium Complexes. General Procedure: 5 mL of a THF
solution of PPh2Li or [(CO)xMЈPPh2]Li (1 mmol) was added drop-
wise at Ϫ80 °C to a solution of [(η6-C6H3-1-F-2-R1Ϫ4-R2)Cr(CO)3]
(1 mmol) in THF (15 mL) in the presence of freshly distilled
HMPT (1 mmol). The stirred mixture was gradually warmed to
room temperature for about 5 h, and THF was then removed in
vacuo. With R3 ϭ PPh2, the crude product was dissolved in toluene
and filtered through Celite. For the dimetallic systems [R3
ϭ
(CO)xMЈPPh2], the residue was washed with pentane and chroma-
tographed (eluent: toluene) to give a yellow powder. All complexes
[(η6-C6H3-1-R3-2-R1-4-R2)Cr(CO)3] were isolated as yellow crys-
tals after recrystallization from acetone.
(Arene)manganese Complexes. General Procedure: 5 mL of a THF
solution of PPh2Li or [(CO)xMЈPPh2]Li (1 mmol) was added drop-
wise to
a
suspension of [(η6-C6H4-2-R1-4-R2)Mn(CO)3](PF6)
(1 mmol) in THF (15 mL) at Ϫ80 °C. The stirred mixture was
gradually warmed to room temperature for about 5 h, and THF
was then removed in vacuo. With R3 ϭ PPh2, the crude product
was dissolved in Et2O and filtered through Celite. For the dimet-
allic systems [R3 ϭ (CO)xMЈPPh2], the residue was washed with
pentane and chromatographed (eluent: toluene) to give an orange-
yellow powder. All complexes [(η5-C6H3-2-R1-4-R2-6-R3)Mn(CO)3]
were isolated after recrystallization from toluene.
[(η6-C6H5-1-PPh2)Cr(CO)3] (5a): Yellow crystals (238 mg, 60%
yield). IR (νCO, THF): ν˜ ϭ 1969 (s), 1899 (s) cmϪ1 1H NMR
.
(CD3COCD3): see Table 2. 31P{1H} NMR (CDCl3): δ ϭ Ϫ1.8 (s)
ppm. C21H15CrO3P (398.3): calcd. C 63.32, H 3.80; found C 62.93,
H 4.08.
[(η6-C6H4-1-PPh2-2-Me)Cr(CO)3] (5b): Not recrystallized (247 mg,
60% yield). IR (νCO, THF): ν˜ ϭ 1971 (s), 1895 (s) cmϪ1. 1H NMR
(CD3COCD3): δ ϭ 2.26 ppm (s, 3 H, Me); see Table 2. 31P{1H}
NMR (CD3COCD3): δ ϭ Ϫ9.8 (s) ppm.
[(η6-C6H4-1-PPh2-4-Me)Cr(CO)3] (5c): Yellow crystals (247 mg,
60% yield). IR (νCO, THF): ν˜ ϭ 1970 (s), 1900 (s) cmϪ1. 1H NMR
(CD3COCD3): δ ϭ 2.23 (s, 3 H, Me), ppm; see Table 2. 31P{1H}
NMR (CDCl3): δ ϭ Ϫ2.9 (s) ppm. C22H17CrO3P (412.3): calcd. C
64.08, H 4.16; found C 63.73, H 3.81.
[(η5-C6H6-6-R3)Mn(CO)3] (R3 ؍ PPh2: 2a): Yellow crystals (60 mg,
40% yield). IR (νCO, THF): ν˜ ϭ 2014 (w), 1935 (s) cmϪ1. 1H NMR
(CD3COCD3): see Table 1. 31P{1H} NMR (CD3COCD3): δ ϭ 9.9
(s) ppm. C21H16MnO3P (402.3): calcd. C 62.70, H 4.01; found C
62.44, H 4.14. {R3 ؍ PPh2Cr(CO)5: 3a[Cr]}: Yellow crystals
(326 mg, 55% yield). IR (νCO, THF): ν˜ ϭ 2061 (m), 2020 (s), 1982
[(η6-C6H5-1-R3)Cr(CO)3] {R3 ؍ PPh2Cr(CO)5: 6a[Cr]}: Yellow
1
(w), 1940 (s) cmϪ1. H NMR (CD3COCD3): see Table 1. 31P{1H}
˜
crystals (501 mg, 85% yield): IR (νCO, THF): ν ϭ 2065 (w), 1978
1
(m), 1943 (s), 1909 (s) cmϪ1. H NMR (CD3COCD3): see Table 2.
NMR (CD3COCD3): δ ϭ 62.8 (s) ppm. C26H16CrMnO8P (594.3):
calcd. C 52.55, H 2.71; found C 52.97, H 2.77. {R3 ؍ PPh2Fe(CO)4:
3a[Fe]}: Yellow crystals (199 mg, 35% yield). IR (νCO, THF): ν˜ ϭ
31P{1H} NMR (CD3COCD3): δ ϭ 61.5 (s) ppm. 13C{1H} NMR
(CDCl3): δ ϭ 232 [s, Cr(CO)3], 221.4 [d, J ϭ 6.4 Hz, Cr(CO)5
trans], 216.7 [d, J ϭ 12.8 Hz, Cr(CO)5 cis], 136.1 (d, J ϭ 36.7 Hz,
Ph ipso), 133.1 (d, Jϭ11 Hz, Ph ortho), 131.4 (s, Ph para), 129.5 (d,
J ϭ 9.2 Hz, Ph meta), 101.5 (d, J ϭ 24.8 Hz, C-1), 99.4 (d, J ϭ
10 Hz, C-2 and C-6), 96.2 (s, C-4), 87.9 (d, J ϭ 6.4 Hz, C-3 and C-
5) ppm. C26H15Cr2O8P (590.4): calcd. C 52.90, H 2.56; found C
52.98, H 2.69.
2053 (m), 1978 (w), 1943 (s) cmϪ1
.
1H NMR (CD3COCD3): see
77.4 (s) ppm.
Table 1. 31P{1H} NMR (CD3COCD3):
δ ϭ
C25H16FeMnO7P (570.2): calcd. C 52.67, H 2.83; found C 52.95,
H 2.58.
[(η5-C6H5-2-OMe-6-R3)Mn(CO)3] {R3 ؍ PPh2Cr(CO)5: 3b[Cr]}:
Yellow crystals (343 mg, 55% yield). IR (νCO, THF): ν˜ ϭ 2061
(m), 2019 (s), 1980 (w), 1940 (s) cmϪ1
.
1H NMR (CD3COCD3): [(η6-C6H4-1-R3-2-Me)Cr(CO)3] {R3
؍
PPh2Cr(CO)5: 6b[Cr]}:
Yellow crystals (483 mg, 80% yield). IR (νCO, THF): ν˜ ϭ 2067 (w),
1972 (m), 1944 (s), 1898 (s) cmϪ1 1H NMR (CD3COCD3): δ ϭ
δ ϭ 3.39 (m, 4 H, OMe and 1-H) ppm, see Table 1. 31P{1H} NMR
(CD3COCD3): δ ϭ 63.4 (s) ppm. C27H18CrMnO9P (624.3): calcd.
.
C 51.92, H 2.88; found C 52.20, H 2.98. {R3 ؍ PPh2Fe(CO)4: 2.11 (s, 3 H, Me) ppm; see Table 2. 31P{1H} NMR (CD3COCD3):
3b[Fe]}: Not recrystallized (329 mg, 55% yield). IR (νCO, THF):
δ ϭ 60.21 (s) ppm. 13C{1H} NMR (CDCl3): δ ϭ 232.5 [s, Cr(CO)3],
ν˜ ϭ 2053 (m), 2018 (f), 1978 (m), 1940 (s) cmϪ1 1H NMR 221.5 (d, Jϭ5.5 Hz, Cr(CO)5 trans), 216.8 (d, J ϭ 12 Hz, Cr(CO)5
.
Eur. J. Inorg. Chem. 2003, 1893Ϫ1899
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1897

V. Comte, J. P. Tranchier, F. Rose-Munch, E. Rose, D. P. P. Richard, C. Mo¨ıse
FULL PAPER
[2] [2a]
A. R. Pape, K. P. Krishna, E. P. Kündig, Chem. Rev. 2000,
cis), 134.9 (d, J ϭ 12 Hz, Ph ortho), 133.9 (d, J ϭ 36 Hz, Ph ipso),
133.1 (d, J ϭ 12 Hz, Ph ortho), 133.0 (d, J ϭ 35 Hz, Ph ipso), 131.9
(s, Ph para), 131.4 (s, Ph para), 129.7 (s, Ph meta), 129.5 (s, Ph
meta), 112.7 (d, J ϭ 8.3 Hz, C-2), 104.7 (d, J ϭ 20 Hz, C-1), 97.9
(d, J ϭ 14.7 Hz, C-6), 97.1 (s, C-4), 92.4 (d, J ϭ 4.6 Hz, C-5), 87.5
(d, J ϭ 6.5 Hz, C-3), 22.4 (s, CH3) ppm. C27H17Cr2O8P (604.4):
calcd. C 53.66, H 2.84; found C 53.57, H 3.02. {R3 ؍ PPh2Fe(CO)4:
6b[Fe]}: Not recrystallized (348 mg, 60% yield). IR (νCO, THF):
[2b]
100, 2917.
G. Bernardinelli, S. Gillet, E. P. Kündig, L.
Ronggang, A. Ripa, L. Saudan, Synthesis 2001, 13, 2040.
J. Breimair, M. Wieser, W. Beck, J. Organomet. Chem. 1992,
441, 429.
B. Niemer, J. Breimair, T. Völkel, B. Wagner, K. Polborn, W.
Beck, Chem. Ber. 1991, 124, 2237.
B. Niemer, M. Steinmann, W. Beck, Chem. Ber. 1988, 121,
1767.
J. Milke, K. Sünkel, W. Beck, J. Organomet. Chem. 1997, 543,
39.
[3]
[4]
[5]
[6]
[7]
[8]
[9]
ν˜ ϭ 2051 (w), 1972 (s), 1943 (s), 1897 (s) cmϪ1 1H NMR
.
(CD3COCD3): δ ϭ 2.16 (s, 3 H, Me) ppm; see Table 2. 31P{1H}
NMR (CD3COCD3): δ ϭ 74.0 (s) ppm.
X. Zhang, G. B. Carpenter, D. A. Sweigart, Organometallics
1999, 18, 4887.
H. Li, G. B. Carpenter, D. A. Sweigart, Organometallics 2000,
19, 1823.
[(η6-C6H4-1-R3-4-Me)Cr(CO)3] {R3
Yellow crystals (362 mg, 60% yield). IR (νCO, THF): ν˜ ϭ 2066 (w),
1973 (m), 1943 (s), 1901 (s) cmϪ1 1H NMR (CD3COCD3): δ ϭ
؍ PPh2Cr(CO)5: 6c[Cr]}:
.
[9a] For insertion of a Pd entity into the CϪCl bond of cationic
Mn complexes, see: J. F. Carpentier, Y. Castanet, J. Brocard, A.
Mortreux, F. Rose-Munch, C. Susanne, E. Rose, J. Organomet.
Chem. 1995, 493, C22. [9b] For insertion of a Pd entity into the
CϪCl bond of Cr complexes, see for example: J. F. Carpentier,
F. Petit, A. Mortreux, V. Dufaud, J. M. Basset, J. Thivolle-
Cazat, J. Mol. Cat. 1993, 81, 1.
2.33 (s, 3 H, Me) ppm; see Table 2. 31P{1H} NMR (CD3COCD3):
δ ϭ 60.5 (s) ppm. 13C{1H} NMR (CDCl3): δ ϭ 231.4 [s, Cr(CO)3],
221.4 (d, J ϭ 6.5 Hz, Cr(CO)5 trans), 216.7 (d, J ϭ 12 Hz, Cr(CO)5
cis), 136.5 (d, J ϭ 37 Hz, Ph ipso), 133.0 (d, J ϭ 10.5 Hz, Ph ortho),
131.3 (s, Ph para), 129.4 (d, J ϭ 9 Hz, Ph meta), 111.9 (s, C-4),
99.9 (d, J ϭ 14.7 Hz, C-2 and C-6), 99.4 (d, J ϭ 27 Hz, C-1), 89.3
(d, J ϭ 6.5 Hz, C-3 and C-5), 21.3 (s, CH3). C27H17Cr2O8P (604.4):
calcd. C 53.66, H 2.84; found C 53.80, H 2.99. {R3 ؍ PPh2Fe(CO)4:
6c[Fe]}: Yellow crystals (330 mg, 57% yield). IR (νCO, THF): ν˜ ϭ
2051 (w), 1976 (s), 1942 (s), 1901 (s) cmϪ1. 1H NMR (CD3COCD3):
[10]
[11]
F. Rose-Munch, C. Susanne-Lecorre, F. Balssa, E. Rose, J.
Vaissermann, E. Licandro, A. Papagni, S. Maiorana, W. Meng,
R. Stephenson, J. Organomet. Chem. 1997, 545.
C. Renard, R. Valentic, F. Rose-Munch, E. Rose, J. Vaisser-
mann, Organometallics 1998, 17, 1587.
δ
ϭ 2.35 (s, 3
H, Me) ppm; see Table 2. 31P{1H} NMR
(CD3COCD3): δ ϭ 78.1 (s) ppm. C26H17CrFeO7P (580.2): calcd. C
[12] [12a]
J. A. Heppert, M. E. Thomas-Miller, P. N. Swepston, M.
W. Extine, J. Chem. Soc., Chem. Commun. 1988, 280. [12b] J. A.
Heppert, M. E. Thomas-Miller, F. Takusagawa, M. A. Morg-
enstern, M. R. Shaker, Organometallics 1989, 8, 1199.
53.82, H 2.95; found C 54.30, H 2.99.
[12c]
G.
Crystal Structure of 6b[Cr]: Single crystals of 6b[Cr] were obtained
by recrystallization from acetone. Intensity data were collected with
a Nonius Kappa CCD at 110 K. The structure was solved with a
Patterson search program and refined with full-matrix least-squares
methods based on F2(SHELXL-97)[25] with the aid of the WINGX
program.[26] All non-hydrogen atoms were refined with anisotropic
thermal parameters. Hydrogen atoms were included in their calcu-
lated positions or found in the final difference Fourier maps and
refined with a riding model. CCDC-187419 contains the sup-
plementary crystallographic data for this paper. These data can be
obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.
html [or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-
1223/336-033; E-mail: deposit@ccdc.cam.ac.uk].
B. Richter-Addo, A. D. Hunter, N. Wichrowska, Can. J. Chem.
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S. Rigny, J.-C. Leblanc, C. Mo¨ıse, New J. Chem. 1995, 19,
[13b]
145.
S. Rigny, J.-C. Leblanc, C. Mo¨ıse, B. Nuber, New J.
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[13d]
J.-C. Leblanc, C. Mo¨ıse, Inorg. Chem. 1996, 35, 3202.
V.
Comte, O. Blacque, M. M. Kubicki, C. Mo¨ıse, Organometallics
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[14] [14a] For the preparation of 1a see: A. M. Munro, P. L. Pauson,
[14b]
Z. Anorg. Allg. 1979, 458, 211.
For preparation of 1b, see:
[14c]
P. L. Pauson, J. A. Segal, J. Chem. Soc. 1975, 1677.
For
the preparation of 1c, see: F. Balssa, V. Gagliardini, F. Rose-
Munch, E. Rose, Organometallics 1996, 15, 4373.
For the preparation of 4a, see:
[15]
[15a]
C. A. L. Mahaffy, J. Or-
ganomet. Chem. 1984, 262, 33. For the preparation of 4b and
4c, see:
[15b]
G. Winkhaus, L. Pratt, G. Wilkinson, J. Chem.
Soc. 1961, 3807.
Acknowledgments
[16]
[17]
PPh2Li was prepared from PPh2H and butyllithium. PPh2H
was prepared by a published procedure: V. D. Bianco, S. Do-
ronzo, Inorg. Synth. 1976, 16, 162.
We thank the CNRS and the European Community TMR program
no. FMRX-CT98-0166 and COST D14 program for financial
support (J. P. T., F. R. M. and E. R.).
The reaction of PPh2Li with [(C6H6)Mn(CO)3]ϩ was already
described: P. J. C. Walker, A. J. Mawby, Inorg. Chim. Acta 1973,
7, 621. However, the corresponding addition product was ob-
tained in a very small amount which, according to the authors,
rendered impossible complete characterisation of the complex
which decomposed during attempted purification.
[1] [1a]
F. Mc Quillin, D. G. Parker, G. R. Stephenson, Transition
Metal, Organometallics for Organic Synthesis, Cambridge Uni-
M. F. Semmelhack,
Comprehensive Organometallic Chemistry (Eds.: W. Abel, F. G.
[1b]
versity Press, Cambridge, 1991, p. 429.
[18] [18a]
[18b]
´
S. Rigny, Thesis, Universite de Bourgogne, 1995.
We
A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, vol. 12,
[1c]
were unable to purify complexes 3c[Fe] and 6a[Fe] for sta-
chapter 9, p. 979.
K. F. McDaniel, Comprehensive Or-
bility reasons.
ganometallic Chemistry (Eds.: E. W. Abel, F. G. A. Stone, G.
Wilkinson), Pergamon, Oxford, 1995, vol. 6, chapter 4, p. 93.
[19]
Such a regioselectivity has been observed for other nucleophiles
[1d]
F. Rose-Munch, V. Gagliardini, C. Renard, E. Rose, Coord.
adding meta to the MeO substituent of the arene ring, see for
[19a]
Chem. Rev. 1998, 178Ϫ180, 249. [1e] R. D. Pike, D. A. Sweigart,
example:
A. J. Pearson, I. C. Richards, J. Organomet.
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[1f]
Coord. Chem. Rev. 1999, 187, 183.
D. Astruc, Chimie Or-
[19c]
´
ganometallique, Ed. EDP Sciences, Les Ulis, France, 2000, p.
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Y. K. Chung, H. K.
[1g]
[19d]
111.
F. Rose-Munch, E. Rose, Eur. J. Inorg. Chem. 2002, 6,
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[1h]
1269.
F. Rose-Munch, E. Rose, Modern Arene Chemistry
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[19e]
(Ed.: D. Astruc), Wiley-VCH, Weinheim, 2002, chapter 11, p.
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1898
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 1893Ϫ1899

Reactivity of Metallophosphides with (Arene)tricarbonylmetal Complexes
FULL PAPER
[22]
F. Balssa, V. Gagliardini, C. Lecorre-Susanne, F. Rose-Munch,
E. Rose, J. Vaissermann, Bull. Soc. Chim. Fr. 1997, 134, 537.
Complex 5a has already been synthesised by treating the lith-
ium derivative of (benzene)tricarbonylchromium complexes
with chloro(diphenyl)phosphane: [20a] W. R. Cullen, S. J. Rettig,
H. Zhang, Can. J. Chem. 1996, 74, 2167. Alternative: transmet-
allation of a stannous derivative of (benzene)tricarbonylchrom-
F. Van Meurs, J. M. A. Baas, H. Van Bekkum, J. Organomet.
Chem. 1976, 113, 353.
J. P. Djukic, F. Rose-Munch, E. Rose, J. Vaissermann, Eur. J.
Inorg. Chem. 2000, 1295 and references therein.
M. J. Breen, P. M. Shulman, G. L. Geoffroy, A. L. Rheingold,
W. C. Fultz, Organometallics 1984, 3, 782.
G. M. Sheldrick, SHELX97, Programs for Crystal Structure
Analysis (includes SHELXS-97, SHELXL-97), release 97-2,
University of Göttingen, Germany, 1998.
L. J. J. Farrugia, Appl. Crystallogr. 1999, 32, 837.
Received September 19, 2002
[20]
[23]
[24]
[25]
ium complexes with nBuLi followed by treatment with chloro-
[20b]
(diphenyl)phosphane:
W. E. Wright, L. Lawson, B. T.
[26]
Baker, D. C. Rae, Tetrahedron 1993, 11, 323.
V. Comte, C. Mo¨ıse, F. Rose-Munch, E. Rose, unpublished re-
sults.
[21]
Eur. J. Inorg. Chem. 2003, 1893Ϫ1899
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1899