Adducts of Mn and Re vinylidenes with P–OR nucleophiles: Hydrolysis rather than the intramolecular Michaelis–Arbuzov rearrangement

Article abstract of DOI:10.1016/j.jorganchem.2017.10.008

The reactions of vinylidene complexes Ср(CO)₂Mn = C=C(H)Ph (Mn1) and Cp(CO)₂Re = C=C(H)Ph (Re1) with P–OR nucleophiles P(OR)R'R" (OR = R' = R" = OMe, OEt, OPrⁱ, OPh; OR = OEt, R' = R" = Ph; OR = R' = OEt, R" = Ph) proceed

Full text of DOI:10.1016/j.jorganchem.2017.10.008

Accepted Manuscript
Adducts of Mn and Re vinylidenes with P–OR nucleophiles: Hydrolysis rather than the
intramolecular Michaelis–Arbuzov rearrangement
Kamil I. Utegenov, Vasily V. Krivykh, Oleg S. Chudin, Alexander F. Smol'yakov, Fedor
M. Dolgushin, Oleg V. Semeikin, Nikolai A. Shteltser, Nikolai A. Ustynyuk
PII:
S0022-328X(17)30584-3
10.1016/j.jorganchem.2017.10.008
JOM 20128
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 22 August 2017
Revised Date: 6 October 2017
Accepted Date: 10 October 2017
Please cite this article as: K.I. Utegenov, V.V. Krivykh, O.S. Chudin, A.F. Smol'yakov, F.M. Dolgushin,
O.V. Semeikin, N.A. Shteltser, N.A. Ustynyuk, Adducts of Mn and Re vinylidenes with P–OR
nucleophiles: Hydrolysis rather than the intramolecular Michaelis–Arbuzov rearrangement, Journal of
Organometallic Chemistry (2017), doi: 10.1016/j.jorganchem.2017.10.008.
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ACCEPTED MANUSCRIPT
Adducts of Mn and Re Vinylidenes with P–OR Nucleophiles: Hydrolysis rather than the
Intramolecular Michaelis–Arbuzov Rearrangement#
Kamil I. Utegenov,a Vasily V. Krivykh,a,* Oleg S. Chudin,b Alexander F. Smol’yakov,a,c Fedor
M. Dolgushin,a Oleg V. Semeikin,a Nikolai A. Shteltser,a and Nikolai A. Ustynyuka,*
#The authors dedicate this paper to Prof. Irina P. Beletskaya, a famous expert in organometallic
chemistry and catalysis.
a A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul.
Vavilova 28, Moscow, 119991 Russian Federation
b Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of
Sciences, ul. K. Marksa 42, Krasnoyarsk, 660049 Russian Federation
c Faculty of Science, RUDN University, ul. Miklukho-Maklaya 6, Moscow, 117198 Russian
Federation
* Corresponding author. E-mail address: ustynyuk@ineos.ac.ru, vkriv@ineos.ac.ru
Abstract
The reactions of vinylidene complexes Ср(CO)2Mn=C=C(H)Ph (Mn1) and
Cp(CO)2Re=C=C(H)Ph (Re1) with P–OR nucleophiles P(OR)R'R" (OR = R' = R" = OMe, OEt,
OPri, OPh; OR = OEt, R' = R" = Ph; OR = R' = OEt, R" = Ph) proceed as nucleophilic addition
to the Cα vinylidene atom to initially afford zwitter-ionic complexes Z-
Ср(CO)2M¯ −C[+P(OR)R'R"]=C(H)Ph which were identified by spectroscopic methods and, in
some cases, their molecular structures were confirmed by X-ray diffraction. These adducts are
extremely sensitive to water and hydrolyzed by water traces to afford the corresponding η2-
phosphorylalkene complexes Cp(CO)2M{η2-E-HC[P(O)R'R"]=C(H)Ph}. The isotopic label
18
experiments with D2O and H2 O showed the hydrolysis to proceed with the phosphorus–oxygen
bond cleavage and binding of the water hydrogen to the carbon atom bearing the >P=O group.
Keywords: transition metal vinylidenes, manganese complexes, rhenium complexes,
alkenylphosphonate complexes, phosphites, quasiphosphonium cations.
1. Introduction
The Michaelis–Arbuzov reaction (hereinafter referred to as the MA reaction) is one of the
universal and well-studied tools for the formation of carbon–phosphorus bonds [1,2]. It is widely
used primarily for the synthesis of phosphonates, phosphinates, and phosphine oxides, but also
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its applications to the synthesis of phosphorus-free organic compounds (alkyl halides [3], ethers
and esters, nitriles, isothiocyanates [4], etc.) via activation of hydroxyl groups in alcohols are
known. The common pathway of the MA reaction is shown in Scheme 1. The ratio between the
rates of nucleophilic substitution at the carbon atom in R4X (a) and the MA nucleophilic
dealkylation in the intermediate quasiphosphonium cation (b) is generally governed by the nature
of R1–R4 and X groups.
Scheme 1
Quasiphosphonium intermediates [R1R2P+(OR3)R4]X– were isolated and completely
characterized in cases where the step (b) is difficult to proceed due to the nature of the R3 group
as for aryloxy (R3 = aryl) [5] and sterically hindered alkoxy derivatives (R3 = neopentyl [6], trityl
[7], and bicyclo[2.2.1]heptyl [8]) or the low nucleophilicity of X– anion (X = ВF4 [9], PPh4 [9k],
SbCl6 [9h,10], etc.); the formation of such intermediates was confirmed in some cases by 31P
NMR spectroscopy [6a,9a,11]. Generally, the MA reactions proceed along paths (a) + (b), but
more rarely there are equilibria between the phosphonium and corresponding five-coordinated
phosphorane structures [12]. To accelerate the MA reaction, it was proposed to use polyethylene
glycol [13] or ionic liquids as solvents [14], ultrasonic activation [15], catalysis by iodine [16] or
Lewis acids (BF3•OEt2 [17], CeCl3•7H2O [18], Me3SiX(X = Br, I, OTf) [17,19]), as well as
catalysis by Group 10 metal compounds to perform the MA reactions with vinyl and aryl halides
[20]. The radical MA reactions are known, but they have not been introduced into synthetic
practice [21,22].
The MA rearrangements can occur also in the transition metal coordination sphere; great
attention was given to the search and study of such processes during the past 30 years and the
main results have been reviewed thoroughly by T. Brill and S. Landon [23]. Typically, such
“organometallic MA rearrangements” occur under milder conditions compared to the classical
MA reactions [24]. Most often, the MA dealkylation (Scheme 1, (b)) proceeds in cationic
transition metal phosphite complexes [LnM-P(OR)3]+X– under the action of the outer-sphere
anion X– to result in organometallic phosphonates LnM-P(О)(OR)2 and organic halides RX. One
approach to these MA precursors is the reaction between highly nucleophilic phosphite
complexes and organic halides [25] (Scheme 2):
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Scheme 2
Although the reaction shown in Scheme 2 is the closest organometallic analogy of the
classical MA reaction, the most of organometallic MA reactions were carried out in a different
manner, viz., the reaction of electrophilic transition metal halide complexes with tertiary
phosphites (Scheme 3). In these reactions, the halide ion is initially replaced to the outer sphere
and then dealkylates the phosphite ligand in the cationic phosphite complex.
Scheme 3
The dihalide complexes can form the corresponding bis-phosphonates as a result of the
double MA reaction [31]. An alternative approach to the MA reaction consists in the initial
isolation of phosphite complexes with a slightly nucleophilic anion {LnM[P(OR)3]}+Y– (Y = BF4
or PF6) (Scheme 3, (a)) followed by their treatment with halide anions, most commonly, iodide
ion [32-34].
The reactions of binuclear carbonyls with tertiary phosphites proceed as radical
organometallic MA reactions (Scheme 4) [35-40].
Scheme 4
The phenomenology of this important reaction have not been established to the full extent
[41,42].
The nucleophilic addition of trialkyl phosphites to electrophilic π-ligands to form
corresponding quasiphosphonium salts is known for the iron ethylene complex [Cp(CO)2Fe(η2-
–
–
H2C=CH2)]+BF4 [43], the iron π-cyclohexadienyl complex [(η5-C6H7)Fe(CO)3]+BF4 and the
–
chromium cycloheptatrienyl complex [(η7-C7H7)Cr(CO)3]+BF4 [44], the iron and ruthenium π-
–
benzene complexes [(η6-C6H6)2M]2+(PF6 )2 (M = Fe, Ru) [45] and the rhodium complex [Rh(η5-
–
C5Me4Et)(η6-C6H6)]+(PF6 )2 [46], as well as for binuclear iron complexes with bridging σ,π-
phenylethynyl Fe2(CO)6(µ-PPh2)(µ-η1:η2-C≡CPh) [47] and allenyl Fe2(CO)6(µ-PPh2)(µ-η1:η2-
C(Н)=С=CН2) [48] ligands. In some cases, the initial adducts underwent spontaneous
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transformation into the corresponding phosphonate complexes [45,46,48]. The same reactions
applied to complexes with multiple metal–carbon bonds proceed differently: the addition of
trimethyl phosphite to the neutral [49,50] and cationic carbene [51,52] and carbyne [53]
complexes affords stable quasiphosphonium adducts.
Among favorable partners for the reaction with P-OR nucleophiles are transition metal
vinylidene complexes. Antonova et al. [54,55] studied the reaction of trialkyl phosphites,
phosphonites, and triphenyl phosphite with the manganese vinylidene complex
Cp(CO)2Mn=C=C(H)Ph (Mn1). These reactions proceed under mild conditions (solvent, 20°C)
to afford reliably identified η2-(Cα-H)-phosphorylalkene complexes B rather than η2-(Cα-R)-
phosphorylakenes C (Scheme 5). In authors' opinion, the reaction proceeds via intermediate
formation of unidentifiable quasiphoshonium compounds A which, in the case of R = OEt,
release the ethylene molecule to form corresponding vinylphosphonates.
Scheme 5
One can state that the reaction pathway for the transformation of intermediate A into product
В remains unclear. Therefore, in the present work we attempted to study in detail the reactions of
the manganese vinylidene complex Cp(CO)2Mn=C=C(H)Ph (Mn1) in order to establish the
structure of intermediate adducts of type A whose formation was proposed by Antonova [54,55]
and to reveal pathways for their subsequent transformations into the phosphorylalkene
complexes of type B.
2. Results and Discussion
2.1.
Synthesis of zwitter-ionic adducts of complex Mn1 and P–OR nucleophiles
We found that the reaction of Mn1 with phosphites P(OR)3 and phosphonite PhP(OEt)2 in a
hydrocarbon solvent in the temperature range from –30°C to –25°C proceeds selectively to form
styrylphosphonium adducts Cp(CO)2Mn––C(+PR'(OR)2)=CHPh (Mn2a-c, Mn3) (Scheme 6)
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which were reliably characterized by spectroscopic methods and, in the case of triethyl phosphite
adduct Cp(CO)2Mn––C[+P(OEt)3]=CHPh (Mn2b), by X-ray diffraction (Fig. 1). It is important
to note that, under low-temperature conditions, the subsequent transformation of the
styrylphosphonium complexes Mn2a-c and Mn3 into the corresponding styrylphosphonate ones
is inhibited almost completely, so that this approach becomes a convenient tool for their
preparation.
Scheme 6
Fig. 1. Molecular structure of Cp(CO)2Mn––C(+P(OEt)3)=CHPh (Mn2b).
The resulting adducts were studied for their behavior in solution. Long-term (24 h) keeping
of Mn2c in a toluene solution at room temperature resulted in its complete transformation into
the styrylphosphonate complex Cp(CO)2Mn{η2-Ph(H)C=CP(O)(OPri)2} (Mn4c) which was
isolated and characterized by IR and 1H and 31P NMR spectroscopy. According to the data from
IR monitoring, complexes Mn2a,b behave like Mn2c on dissolution in toluene (Scheme 7),
whereas complex Mn3 rearranges into Cp(CO)2Mn{η2-Ph(H)C=C(H)-P(O)(OEt)Ph} (Mn5)
much slower, so that, on keeping Mn3 in toluene for 2 h, no changes in the IR spectrum were
observed and, only on keeping in acetone for 18 h, complete transformation into the
styrylphosphonate product Mn5 was achieved.
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Scheme 7
Next, we focused on the reactions between P–OR nucleophiles and the rhenium vinylidene
complex Cp(CO)2Re=C=C(H)Ph (Re1) which was found to afford more stable
quasiphosphonium adducts (Re2a-c, Re3, and Re4, see Scheme 8) to allow studying their
subsequent transformations in details by NMR spectroscopy (in contrast to the manganese
analogs, the rhenium complexes on long-term keeping in a solution do not produce paramagnetic
impurities).
2.2. Synthesis of zwitter-ionic adducts of complex Re1 and P–OR nucleophiles
The reactions of Re1 with tertiary phosphites P(OR)3 (R = Et, Me, Pri), diethyl
phenylphosphonite PhP(OEt)2, and ethyl diphenylphosphinite Ph2P(OEt) proceed in hexane at
room temperature (Scheme 8). Adducts Re2а-с, Re3, and Re4 forming orange crystalline
precipitates were obtained in high yields and characterized by IR spectroscopy, 1H and 31P NMR
13
spectroscopy, elemental analysis, and, in some cases, C NMR spectroscopy. The difference in
the rate of addition of the phosphorus nucleophile to Mn1 and Re1 is quite distinct. For example,
while the addition of P(OEt)3 to the rhenium complex Re1 occurs by 50 % within 2 h at room
temperature, the analogous reaction between triethyl phosphite and Mn1 under the same
conditions affords approximately a 1 : 1 ratio of the starting vinylidene complex to the adduct
Mn1/Mn2a immediately after addition of P(OEt)3.
Scheme 8
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The molecular geometry of the triethyl phosphite adduct Re2b was determined by X-ray
diffraction (Fig. 2). The same was done for Re2а whose crystallographic data are given in Table
1 and the Supporting Information (see Table 1S).
Fig. 2. Molecular structure of Cp(CO)2Re−C[P+(OEt)3]=CHPh (Re2b).
2.3. Transformations of quasiphosphonium rhenium adducts into corresponding
phosphorylalkene complexes
The quasiphosphonium adducts Re2а-с, Re3, and Re4 transform into η2-phosphorylalkene
complexes Re5а-с, Re6, and Re7, respectively on long-term keeping in hexane (Scheme 9).
Scheme 9
1
The η2-phosphorylalkene complexes Re5а-с, Re6, and Re7 were characterized by IR, H,
31
13C, and P NMR spectroscopy and elemental analysis. The molecular geometry of complex
Re5b was determined by X-ray diffraction (Fig. 3)
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Fig. 3. Molecular structure of Сp(CO)2Re(η2-PhСH=CHP(O)(OEt)2) (Re5b).
In all crystallographically characterized structures, the metal atom has normal piano stool
surrounding including the Cp ligand, two linear carbonyl groups, and the σ-linked carbon atom
bearing the phosphoniostyryl group in the “adduct” or the π-coordinated olefin group in the
“product”. The comparison of similar manganese and rhenium complexes Mn2b and Re2b
shows that all bonds involving the metal atom are elongated on going from the former to the
latter. In addition, a slight elongation of the C=C and C–P bonds is observed, which is explained
by a higher π-donating ability of rhenium compared to manganese. Upon comparison of Re2b
and Re5b, all parameters remain unchanged except for consistent elongation of the olefinic bond
upon π-coordination and elongation of the Re-Cπ bonds compared to the Re-Cσ one. The
replacement of P(OEt)3 with PMePh2 [56] in the rhenium “adduct” results in the anticipated
elongation of the bond between the phosphorus atom and the olefinic carbon atom, but has no
effect on the lengths of olefinic and Re-CC(P)=C bonds.
Table 1. Selected bond lengths in complexes Mn2b, Re2a,b, and Re5b and their comparison
with analogous data for the styrylphosphonium adduct Cp(CO)2Re––C(+PMePh2)=C(H)Ph [56]
[Re]––C(+PMePh2)=C(H)Ph
M=Re, R=PMePh2
Compound
Mn2b
M=Mn,
Re2b
M=Re,
Re2a
M=Re,
Re5b
M=Re1),
R=P(O)(OEt)2
1.95
R=P(OEt)3 R=P(OEt)3
R=P(OMe)3
1.97
2)
M-XCp
1.78
1.97
1.96
M-CCO
M-CC(P)=C
M-CC(Ph)=C
C=C
1.751(3),
1.748(3)
2.038(3)
1.881(3),
1.872(3)
2.148(2)
1.886(2),
1.878(2)
2.146(2)
1.882(8)-
1.906(8)
2.235(7),
2.229(7)
2.209(7),
2.225(7)
1.430(9),
1.426(10)
1.759(6),
1.766(6)
1.883(4), 1.873(4)
2.151(3)
1.351(4)
1.737(3)
1.369(3)
1.759(2)
1.366(3)
1.756(2)
1.362(5)
1.796(4)
C-P
1) The data for two independent molecules are given.
2)
X
is the Cp ring centroid.
Cp
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Like the manganese complex Cp(CO)2Mn{η2-Ph(H)C=CP(O)(OEt)Ph} (Mn5) [55], its
rhenium analog Re6 exists as a mixture of diastereomers having identical configuration at the
chiral plane of alkene ligand and different configuration of the phosphorus atom. According to
the 1H and 31P NMR data, the ratio of diastereomers is about 70 : 30.
The preparative-scale synthesis of η2-phosphorylalkene complexes does not require isolation
of the precursor adducts; it is more convenient to stir for a long time a mixture of the vinylidene
complex and the P-OR nucleophile in hexane or to dilute the stirred mixture with wet diethyl
ether; in the latter case, the reaction proceeds faster. In the case of less nucleophilic P–OR
derivatives, the reaction occurs under more severe conditions. For example, triphenyl phosphite
in the reaction with Re1 affords no isolated adduct Re8, but produces a styrylphosphonate
derivative Re9 in yield of 50% upon long-term (50 h) refluxing in hexane (Scheme 10).
Scheme 10
The IR spectra of the mixture recorded during the reaction display the metal-carbonyl bands
for the starting compound Re1 and the final product Re9 only and no metal-carbonyl bands for
intermediate Re8. We assume that the equilibrium at the step of nucleophilic addition is shifted
in favor of dissociation of Re8 into initial compounds Re1 and P(OPh)3, so that the rate of
subsequent irreversible transformation of Re8 into complex Re9 is limited by a low content of
Re8 in solution.
In order to understand more deeply the transformation of quasiphosphonium adducts into
corresponding phosphorylalkene derivatives, we studied the behavior of Cp(CO)2Re––
1
31
C[+P(OEt)3]=CHPh (Re2b) in deuterated benzene in a sealed NMR tube by H and P NMR
spectroscopy. The 1H and 31P spectra for Re2b 10 min after dissolution contain one set of signals
corresponding to the established structure of Re2b. The NMR spectra recorded 24 h after
dissolution showed the presence of two signal sets one of which corresponds to the starting Re2b
and the second one corresponds to the π-styrylphosphonate complex Cp(CO)2Re[η2-Е-
PhCH=CHP(O)(OEt)2] (Re5b). The Re2b/Re5b ratio at this time was 74 : 26. It is worthy of
note that the spectrum contains no signals for Re1 and free triethyl phosphite as the dissociation
products of Re2b, so that the equilibrium at the formation step of Re2b is totally shifted in favor
of the adduct. After 48 h, the contents of complexes Re2b and Re5b were 57% and 43%,
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respectively. From then on, there were a slow decrease in the intensities of signals for the
quasiphosphonium adduct Re2b and a simultaneous increase in the intensities of signals for the
π-styrylphosphonate complex Re5b. However, even one month after the sample preparation, no
complete disappearance of the signals for complex Re2b occurred and the observed Re2b/Re5b
ratio was 12 : 88. It should be noted that, in an open system, this reaction proceeds to
completion, which suggests the presence of water in the system to be a necessary condition for
the reaction. Indeed, upon addition of water to a solution of Re2b in deuterated benzene the
reaction is completed within several days, i.e. significantly faster.
The 1H NMR monitoring of the transformation of adduct Cp(CO)2Re¯–
C{+P(OEt)Ph2}=CHPh (Re4) into the corresponding η2-alkene complex Cp(CO)2Re(η2-
НC{P(O)Ph2}=CHPh (Re7) in a sealed NMR tube in benzene-d6 showed the appearance of
proton signals for Re7 and ethanol. The hydroxyl proton of ethanol appears as a triplet (δ 3.49)
3
with a typical spin-spin coupling constant of J(HOCH ) = 4 Hz. Integration of the ethanol signals
2
shows that its yield corresponds to that of Re7. The addition of ethanol to the NMR tube at this
step results in a significant increase in the intensities of the corresponding resonances. It is
important to note that no signals for ethylene whose formation was proposed earlier [54] were
observed.
The formation of ethanol during transformations of rhenium quasiphosphonium adducts
(Scheme 9) suggest them to proceed under the action of unavoidable water traces as the external
agent. One can assume that the formation of η2-alkene derivatives occurs through the hydrolysis
of ethoxyphosphonium fragments, one of the water hydrogen atoms binding to the phosphoryl-
bearing carbon atom in the η2-alkene complexes. To verify this hypothesis, we performed the
18
reactions of Re4 with D2O and H2 O and the data obtained agree with this assumption. The
reaction of Re4 with D2O affords complex d1-Re7 enriched by deuterium at the Cα-H bond (the
18
18
D/H ratio was 65:35), while the reaction of Re4 with H2 O resulted in product O-Re7 where
the Р=O bond is enriched by the 18O isotope (Scheme 11), which follows from the appearance of
new band at 1147 cm–1 (P=18O) shifted to the low-frequency region compared to the value of
1178 cm-1 for Р=16O (the 18O/16O ratio was about 60:40), as well as from the presence of a peak
at m/z 306 in the mass spectrum of Re7 (cf. m/z 304 for the molecular peak of
diphenylstyrylphosphine oxide).
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Scheme 11
Thus, during the hydrolysis of rhenium quasiphosphonium adducts the oxygen atom of water
binds to the phosphorus atom of the adduct and one of the hydrogen atoms of water binds to the
carbon atom bearing the phosphoryl group in the product. That is, the phosphorus–oxygen bond
cleavage occurs in the same manner as in the case of hydrolysis of alkoxyphosphonium salts
[57]. Therefore, one can assume two pathways for this process (Scheme 12, paths (1) and (2))
Ph
Ph
Ph
H
C
Ph
H
H
H
H
[M]
H
C
P
C
C
C
C
(d)
~H
[M]
H
C
[M]
H
C
[M]
[M]
P
Ph
(a)
(b)
*O
(c)
(1)
C
C
C
C
RO
RO
RO
O*
P
O*
P
H2O*
H
OR
H2O*
H
P
–ROH
–H2O*
H
H
O*
H
*O
OR
OR
H
E
D
F
G
H
Ph
Ph
Ph
Ph
H
H
H
C
[M]
C
H
H
[M]
P
C
C
C
C
Ph
(e)
(f)
(h)
(g)
[M]
H
[M]
H
[M]
H
(2)
C
P
C
P
C
O*
P
H
2 H2O*
H
–ROH
–H2O*
O
*
H
OR
P
O
*
D
*O
O*
H
J
K
I
H
Ph
Ph
H
Ph
H
C
H
C
C
[M]
P
[M]
Ph
(i)
[M]
C
[M]
C
P
(k)
(j)
C
(3)
C
H
R
R
R
P
P
O
O
O
D
L
M
N
Scheme 12
The first step in the hydrolysis of Мn,Re2а-с, Мn,Re3, and Re4 is the addition of the water
oxygen atom to the quasiphosphonium phosphorus atom (Scheme 12.1 (a) and 12.2 (e)). The
adducts formed have two basic centers (metal atom and oxygen atom of ethoxy groups) capable
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of acting as proton acceptors upon hydrogen bonding with the water protons. Correspondingly,
in the initial adduct the “oxonium” hydrogen atoms as proton-donating components are hydrogen
bonded to either the metal atom (Scheme 12.1, (а), adduct E) or the oxygen atom of ethoxy
groups (Scheme 12.2, (e), adduct I). In the first case, the hydrolysis can proceed as hydrogen
transfer to the metal to form corresponding hydrides F, C,H-reductive elimination, and
elimination of alcohol induced by the addition of an additional water molecule [58] (Scheme
12.1, (b) + (c) + (d)). This reaction pathway is justified first by Mn---HO−P+R3 hydrogen
bonding in the structurally closed zwitter-ionic styryl(hydroxy)phosphonium adducts
Cp(CO)2M‾−C(+PR2−ОН)=C(H)Ph [59] and second by a low-barrier and exothermic C,H-
reductive elimination in the structurally close hydrido-phosphoniostyryl derivative
Cp(CO)2(Н)M−C(+PR3)=C(H)Ph [56,59]. The alternative path includes the initial elimination of
alcohol to form a zwitter-ionic adduct J where the hydroxyl hydrogen is hydrogen bonded to the
metal atom (Scheme 12.2, (f)). As we have shown earlier, such zwitter-ionic adducts are
produced upon the addition of hydrosphosphoryl compounds to the vinylidene complexes Mn1
and Re1 and readily transform to the reaction product H [59]. The discrimination between two
reaction pathways shown in Schemes 12.1 and 12.2 requires an additional study. It should be
noted that the third possible reaction pathway, the intramolecular MA dealkylation to form
Сα(R)-styrylphosphonate N (Scheme 12.3), is not realized. Such intermolecular MA dealkylation
in organic zwitter-ionic adducts of phosphites with unsaturated systems is known by few
examples [60].
Thus, the nucleophilic addition of P–OR nucleophiles to the vinylidene complexes Mn1 and
Re1 results in the zwitter-ionic quasiphosphonium adducts Mn2a-c,3 and Re2a-c,3,4 (Schemes
6 and 8) whose spontaneous hydrolysis (Scheme 12) occurs on exposure to trace impurities of
water. This gives reason to believe that the hydrolysis of the initial adducts is the most rapid step
of this process, which, in turn, is due to rapid proton migrations along the routes denoted as
hydrogen bonds (Schemes 12.1 (a) and 12.2 (е)). Reports on analogous spontaneous hydrolysis
of organometallic quasiphosphonium adducts occurring without addition of water could be
mentioned [45,46,48]. Such spontaneous hydrolysis can be suppressed using a dehydrating
agent: for example, the authors of [48] used PhC≡CLi to suppress the hydrolysis of the
quasiphosphonium group in adducts Fe2(CO)6(µ-PPh2)(µ-η1:η2-(CH3)С=C{P(OR)3}) (R = Me,
Et).
On possible catalytic applications
Recently, we have shown that the reaction of manganese and rhenium vinylidene complexes
Mn1 and Re1 with tautomeric hydrophosphoryl compounds HP(O)R2 proceeds according to
12

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Scheme 13, (а)-(с) to result in the η2-phosphorylalkene complexes Cp(CO)2M(η2-E-
HC[P(O)R2]=CHPh) [59].
Scheme 13
As the present study shows, the same complexes H can be obtained from the same
vinylidene complexes Mn1 and Re1 and P-OR nucleophiles (Scheme 13, (d)-(e)). While the first
steps in these processes are similar: reversible nucleophilic addition of the phosphorus
nucleophile to the Cα vinylidene atom, the subsequent steps of reactions are different due to
different structures of initial adducts О and D. In the former adducts, a fast hydrogen transfer can
occur due to hydrogen bonding between the hydroxyl hydrogen and the metal to afford
corresponding hydrides Р followed by C,H-reductive elimination to form the reaction product H
(Scheme 13, (b) + (с)). In the case of P–OR adducts D, they undergo fast hydrolysis,
presumably, according to Schemes 12.1 or 12.2 considered above.
Since Mn1 was reported to catalyze hydrophosphorylation of phenylacetylene with diethyl
phosphite (Scheme 14, (a)) [59], there are ample grounds for assuming that this complex can also
catalyze the hydrolytic phosphorylation of terminal alkynes with trialkyl phosphites or other P-
OR nucleophiles (Scheme 14, (b)).
RC≡CH + HP(O)(ОR1)2 → E-R(H)C=C(H)-P(O)(ОR1)2
(a)
RC≡CH + P(OR1)3 + H2O → E-R(H)C=C(H)-P(O)R1 + R1OH (b)
2
Scheme 14
The search of such catalysis will be the subject of our future studies.
3. Conclusions
Thus, we have shown that the reaction of the vinylidene complexes Re1 and Mn1 with
trialkyl phosphites, diethyl phenylphosphonite, and ethyl diphenylphosphinite result in the
isolated and spectroscopically characterized quasiphosphonium adducts Mn2a-c, Mn3 (Scheme
6) and Re2a-c, Re3, Re4 (Scheme 8) as first rapid step of nucleophilic addition to the Cα
vinylidene atom and their hydrolysis on exposure to water traces to form the η2-
13

ACCEPTED MANUSCRIPT
phosphorylalkyene complexes Mn4a-c, Mn5 and Re5a-c, Re6, Re7 at the second slow step.
Based on the data from experiments with isotopically labeled water, possible reaction pathways
including the phosphorus–oxygen bond cleavage and binding of water hydrogen to the
phosphoryl-bearing carbon atom were proposed.
4. Experimental
4.1
General
All reactions were performed in an argon atmosphere using the Schlenk technique. Low-
temperature experiments were performed using an ethanol−dry ice mixture as the cooling liquid.
The commercially available diethyl ether, benzene, and toluene were dried over sodium
benzophenone ketyl and distilled immediately prior to use. Hexane used to perform the reaction
was distilled over sodium benzophenone ketyl. Other saturated hydrocarbons (pentane,
petroleum ether), dichloromethane, and triethylamine were distilled over CaH2. Acetone was
purified from organic impurities by adding small portions of KMnO4 at reflux until the violet
color persists and dried with freshly annealed K2CO3. Benzene-d6 was distilled over Na/K alloy.
18
18
D2O (99.9 atom % of D) and H2 O (99.9 atom % of O) were purchased from Sigma-Aldrich.
The commercially available silica gel (70−230 mesh, 60 Å, Aldrich) was evacuated and saturated
with inert gas immediately prior to use. P(OMe)3 and P(OPh)3 were purchased from Acros and
used as received. P(OEt)3 [61], P(OPri)3 [62], PPh(OEt)2 [63], and PPh2(OEt) [64] were
synthesized by the reaction of PCl3 or chlorophosphines (PPhCl2, PPh2Cl) with the
corresponding alcohols (EtOH, PriOH) according to the described procedures.
IR spectra were recorded on a Specord M80 IR spectrophotometer (Carl Zeiss, Germany).
13
31
1H, 31P, and C NMR spectra were measured on Bruker Avance 300 (1H at 300.1 MHz and P
31
13
at 121.5 MHz), Bruker Avance 400 (1H at 400.1 MHz, P at 161.98 MHz, and C at 100.58
MHz), and Bruker Avance 600 instruments (13C at 150.93 MHz) using residual signals of
deuterated solvents as the internal standard. Elemental analysis was performed on a Carlo Erba
1106 CHN analyzer.
X-ray Diffraction Study. Single-crystal X-ray diffraction experiments were carried out on a
Bruker SMART APEX II diffractometer (graphite-monochromated MoKα radiation, λ = 0.71073
Å, ω-scan technique). The APEX II software [65] was used for collecting frames of data,
indexing reflections, determination of lattice constants, integration of intensities of reflections,
scaling and absorption correction, while the SHELXTL software [66] was applied for space
group and structure determination, refinements, graphics, and structure reporting. The structures
were solved by direct methods and refined by the full-matrix least-squares technique against F2
with anisotropic thermal parameters for all non-hydrogen atoms. Hydrogen atoms were placed
14

ACCEPTED MANUSCRIPT
geometrically and included in the structure factors calculation in the riding motion
approximation. Crystallographic data for complexes Mn2b, Re2a,b, and Re5b are given in the
Supporting Information (Table 1S and CIF files).
4.2
vinylidene complex Re1 with P–OR nucleophiles
4.2.1
Cp(CO)2Mn––C[P+(OМе)3]=CHPh (Mn2a)
Synthesis of adducts of the manganese vinylidene complex Mn1 and the rhenium
To a cooled to –25°C solution of complex Mn1 (20 mg, 0.072 mmol) in hexane (2 mL),
P(OMe)3 (8.5 µL, 0.072 mmol) was added dropwise. The reaction mixture was agitated and kept
in a freezer (–25°C) over 48 h. The precipitated red-orange crystals were separated from a
mother liquor by decantation and dried in oil-pump vacuum to yield 20 mg (69%) of complex
Mn2a. IR (toluene), νCO/cm–1: 1900 s, 1832 s. 1H NMR (C6D6), δ: 3.22 (d, 9H, 3JHP = 10.8 Hz,
POCH3), 4.30 (s, 5H, Cp), 7.06 (t, 1H, 3JHH = 6.6 Hz, Hpara Ph), 7.31 (dd, 2H, 3JHH = 6.8 Hz,
Hmeta Ph), 8.17 (d, 2H, 3JHH = 6.4 Hz, Hortho Ph), 8.55 (d, 1H, 3JPH = 43.8 Hz, =CHPh). 31P{H}
NMR (C6D6), δ: 37.24 (P+(OMe)3).
4.2.2
Cp(CO)2Mn––C[P+(OEt)3]=CHPh (Mn2b) was obtained as described for Mn2а in
yield of 51 mg (71%) as red-orange crystals from a solution of complex Mn1 (45 mg, 0.162
mmol) in hexane (6 mL) and P(OEt)3( 29 µL, 0.170 mmol). IR (toluene), νCO/cm–1: 1896 s, 1828
s. 1H NMR (C6D6), δ: 0.99 (t, 9H, 3JHH = 6.4 Hz, POCH2CH3), 3.83 (quintet (dq), 6H,
POCH2CH3), 4.34 (s, 5H, Cp), 7.12 (t, 1H, Hpara Ph overlaps with the solvent signal), 7.32 (dd,
2H, 3JHH = 6.6 Hz, Hmeta Ph), 8.21 (d, 2H, 3JHH = 6.9 Hz, HorthoPh), 8.64 (d, 1H, 3JPH = 43.5 Hz,
=CHPh). 31P{H} NMR (C6D6), δ: 33.96 (P+(OMe)3).
The molecular structure of complex Mn2b was also confirmed by X-ray diffraction.
4.2.3
Cp(CO)2Mn––C[P+(OiPr)3]=CHPh (Mn2c) was obtained as described for Mn2а in
yield of 59 mg (75%) as red-orange crystals from a solution of complex Mn1 (45 mg, 0.162
mmol) in hexane (4 mL) and P(OPri)3 (40 µL, 0.162 mmol). IR (toluene), νCO/cm–1: 1896 s, 1828
s. 1H NMR (C6D6), δ: 1.13 (d, 18H, 3JHH = 6.1 Hz, POCH(CH3)2), 4.36 (s, 5H, Cp), 4.82 (m, 3H,
POCH(CH3)2), 7.13 (t, 1H, Hpara Ph overlaps with the C6D6 signal), 7.34 (dd, 2H, 3JHH = 7.3 Hz,
Hmeta Ph), 8.20 (d, 2H, 3JHH = 7.3 Hz, Hortho Ph), 8.62 (d, 1H, 3JPH = 44.0 Hz, =CHPh). 31P{H}
NMR (C6D6), δ: 32.87 (P+(OPri)3).
4.2.4
Cp(CO)2Mn––C[P+Ph(OEt)2]=CHPh (Mn3) was obtained as described for Mn2а in
yield of 43 mg (74%) as orange crystals from a solution of complex Mn1 (34 mg, 0.122 mmol)
in hexane (3 mL) and PPh(OEt)2 (25 µL, 0.128 mmol). Calculated for C25H26MnPO4, %: C,
63.03; H, 5.50. Found, %: C, 62.94; H, 5.41. IR (toluene), νCO/cm–1: 1900 s, 1828 s. 1H NMR
(C6D6), δ: 0.92 (t, 6H, 3JHH = 7.4 Hz, POCH2CH3), 3.33-3.46 (2 dq, 2H, POCH2CH3), 3.67-3.80
15

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(2 dq, 2H, POCH2CH3), 3.92 (2 overlapping s, 5H, Cp), 7.06 (m, 3H, Hpara and Hmeta PPh), 7.12
(m, 1H, 3JHH = 7.4 Hz, Hpara =CHPh), 7.36 (dd, 2H, 3JHH = 7.8 Hz, Hmeta =CHPh), 7.81-7.88 (2
m, 2H, Hortho PPh), 8.34 (d, 2H, 3JHH = 7.8 Hz, Hortho Ph), 9.05 (d, 1H, 3JPH = 40.8 Hz, =CHPh).
31P{H} NMR (C6D6), δ: 38.05, 38.2 (1P each from two isomers, P+Ph(OCH2CH3)2).
4.2.5
Cp(CO)2Re––C[P+(OМе)3]=CHPh (Re2a)
To a red solution of complex Re1 (42.5 mg, 0.104 mmol) in hexane (3 mL), P(OMe)3 (13.5 µL,
0.1144 mmol) was added dropwise with stirring. The mixture was stirred for 3 h and kept for 24
h in a freezer (–25°C). The precipitated orange crystals were separated from a mother liquor by
decantation, washed with cold pentane, and dried in oil-pump vacuum to yield 46 mg (83%) of
product Re2a as bright-orange crystals. Calculated for C18H20O5PRe, %: C, 40.52; H, 3.78.
Found, %: C, 40.50; H, 3.72. IR (toluene), νCO/cm–1: 1896, 1824. 1H NMR (C6D6), δ: 3.32 (d,
9H, 3JPH = 11.3 Hz, POCH3), 4.72 (s, 5H, Cp), 7.10 (t, 1H, 3JHH = 7.6 Hz, Hpara Ph), 7.22 (dd,
2H, 3JHH = 7.8 Hz, Hmeta Ph), 7.99 (d, 2H, 3JHH = 7.1 Hz, Hortho Ph), 8.45 (d, 1Н, =CH, 3JPH =
40.6 Hz). 31P{H} NMR{1H} (C6D6), δ: 35.01 (s, –+P(OMe)3).
The molecular structure of complex Re2a was also confirmed by X-ray diffraction.
Complex Re2a was found to be quite stable in air and slowly transformed into the corresponding
phosphorylstyrene complex Cp(CO)2Re{η2-PhCH=CHP(O)(OMe)2} (Re5a): keeping a residue
after evaporation of a toluene solution for 3 days in air at room temperature resulted in complete
transformation of Re2a into Re5a. IR (toluene), νCO/cm–1: 1984 s, 1916 s. 31P{H} NMR (C6D6),
δ: 36.99 (s, P(O)(OMe)2).
4.2.6
Cp(CO)2Re––C[P+(OEt)3]=CHPh (Re2b)
To a solution of complex Re1 (40 mg, 0.098 mmol) in hexane (3 mL), P(OEt)3 (18 mg,
0.108 mmol) was added and stirred for 2.5 h. The course of the reaction was monitored by IR
spectroscopy. The reaction mixture was cooled to –25 °C and kept for 24 h at this temperature.
The bright-orange precipitate that formed was filtered off, washed with cold petroleum ether, and
dried in the stream of argon to yield 44 mg (78%) of product Re2b as light-yellow crystals.
Calculated for C21H26O5PRe, %: C, 43.82; H, 4.55. Found, %: C, 43.67, H, 4.55. IR, ν/cm–1:
(hexane) 1900s, 1830s (CO); (CH2Cl2) 1885s, 1815s (CO); (C6H6) 1890s, 1820s (CO). 1H NMR
(C6D6), δ: 1.08 (t, 9Н, 3JHH = 7.0 Hz, POCH2CH3), 4.00 (dq, 6H, 3JHH ≈ 3JPH ≈ 7.0 Hz,
POCH2CH3), 4.85 (s, 5H, Cp), 7.15 (t, 1H, 3JHH = 7.5 Hz, Hpara Ph), 7.32 (dd, 2H, 3JHH = 7.6 Hz,
Hmeta Ph), 8.17 (d, 2H, 3JHH = 7.7 Hz, Hortho Ph), 8.70 (d, 1Н, =C2H, 3JPH = 41.2 Hz). 13C{H}
NMR (C6D6), δ: 15.65 (d, 3JCP = 6.9 Hz, POCH2CH3), 65.40 (d, POCH2CH3, 2JCP = 8.4 Hz),
84.31 (s, Cp), 120.55 (d, 1JCP = 62.0 Hz, PC=CHPh), 127.22 (s, Cpara Ph), 129.22 (d, 4JCP = 2.3
16

ACCEPTED MANUSCRIPT
Hz, Cortho Ph), 142.71 (d, 2JCP = 42.8 Hz, PC=CHPh), 158.28 (d, 3JCP = 10.7 Hz, Cipso Ph), 208.5
(s, CO). 31P{H} NMR (C6D6), δ: 32.0 (s, +P(OEt)3).
The molecular structure of Re2b was confirmed by single crystal X-ray diffraction.
4.2.7
Cp(CO)2Re––C[P+(OPri)3]=CHPh (Re2с)
To a solution of complex Re1 (20 mg, 0.049 mmol) in hexane (1 mL), P(OPri)3 (11 mg, 0.053
mmol) was added and stirred for 2 h. The reaction mixture was kept at 5 °C for 12 h. The bright-
orange precipitate was filtered off, washed with cold petroleum ether, and dried in oil-pump
vacuum to yield 26 mg (86%) of product Re2c as light-yellow crystals. Calculated for
C24H32O5PRe, %: C, 46.67; H, 5.22. Found, %: C, 46.60; H, 5.25. IR (hexane), ν/cm–1: 1895s,
1
3
1825s (CO). H NMR (C6D6), δ: 1.23 (d, 18 H, JHH = 6.2 Hz, PCH(CH3)2), 4.82 (s, 5H, Cp),
5.11 (m, 3 H, PCH(CH3)2) 7.15 (t, 1H, 3JHH = 7.2 Hz, Hpara С6Н5), 7.31 (dd, 1H, 3JHH = 7.5 Hz,
3
3
31
Hmeta С6Н5), 8.09 (d, JHH = 7.3 Hz, Hortho Ph), 8.69 (d, 1Н, JPH = 40.5 Hz, =CHPh). P{H}
NMR (C6D6), δ: 29.56 [P(OPri)3]. 13C{H} NMR (C6D6), δ: 23.74 (d, 4JCP = 4.5 Hz, PCH(CH3)2),
3
75.92 (d, JCP = 9.8 Hz, PCH(CH3)2), 84.31 (s, Cp), 123.13 (d, JCP = 62.7 Hz, PC=CHPh),
4
2
127.09 (s, CparaPh), 129.42 (d, JCP = 1.5 Hz, CorthoPh), 143.43 (d, JCP = 41.6 Hz, PC=CHPh),
157.80 (d, 3JPH = 11.3 Hz, CipsoPh), 209.14 (s, CO).
4.2.8
Cp(CO)2Re––C[P+Ph(OEt)2]=CHPh (Re3)
To a solution of complex Re1 (20 mg, 0.049 mmol) in hexane (3 mL), PhP(OEt)2 (11 mg, 0.056
mmol) was added. The reaction mixture was stirred for 10 min at room temperature and kept for
2 h at –25°C. The precipitated light-yellow crystals were filtered off, washed with cold
petroleum ether, and dried in oil-pump vacuum to yield 27 mg (91%) of product Re3 as light-
yellow crystals. Calculated for C25H26O4PRe, %: C, 49.42; H, 4.31. Found: C, 49.50; H, 4.37. IR
(hexane), ν/cm–1: 1900s, 1835s (CO). 1H NMR (C6D6), δ: 1.04 (t, 6Н, 3JHH = 7.1 Hz, OCH2CH3),
3.56 (m, 2H, OCH2CH3), 3.94 (m, 2H, OCH2CH3), 4.51 (s, 5H, Cp), 7.10-7.16 (m, 3H, Hmeta and
3
3
Hpara =CHPh); 7.2 (t, JHH = 7.3 Hz, Hpara PPh); 7.37 (dd, 2H, JHH = 7.7 Hz, Hmeta PPh); 7.93
(m, 2H, Hortho PPh), 8.39 (d, 3JHH = 7.4 Hz, Hortho =СHPh), 9.07 (d, 1Н, 3JPH = 38.1 Hz, =CHPh).
4.2.9
Cp(CO)2Re––C[P+Ph2(OEt)]=CHPh (Re4).
To a solution of complex Re1 (40 mg, 0.098 mmol) in hexane (1 mL), Ph2P(OEt) (25 mg, 0.109
mmol) was added. The reaction mixture was stirred for 2 h. The precipitate formed was filtered
off and dried in oil-pump vacuum to yield 48 mg (77%) of product Re4 as light-yellow powder.
Calculated for C29H26O3PRe, %: C, 54.45; H, 4.10. Found: C, 54.40; H, 4.12. IR (hexane), ν/cm–
1
3
1: 1902s, 1835s (CO). H NMR (C6D6), δ: 0.89 (t, 3H, JHH = 7.0 Hz, OCH2CH3), 3.43 (dq, 2H,
3
3JHH ≈ JPH ≈ 6.4 Hz, POCH2CH3), 4.44 (s, 5H, Cp), 7.11-7.23 (Hpara Ph; Hmeta and Hpara PPh),
7.39 (dd, 2H, 3JHH = 7.6 Hz, Hmeta Ph), 8.02 (d, 2H, 3JHH = 7.9 Hz, Hortho PPh), 8.06 (d, 2H, 3JHH
17

ACCEPT3ED MANUSCRIPT
3
= 7.2 Hz, Hortho PPh), 8.37 (d, 2H, JHH = 7.7 Hz, Horhto Ph), 8.75 (d, 1Н, JPH = 39.0 Hz,
=CHPh). 31P{H} NMR (C6D6), δ: 32.28 (s, P+Ph2(OEt)).
4.3
Manganese and rhenium η2-phosphorylalkene complexes
4.3.1
Cp(CO)2Mn{η2-PhCH=CHP(O)(OiPr)2} (Mn4c)
To a cooled to –25°C solution of complex Mn1 (45 mg, 0.162 mmol) in hexane (4 mL), P(OPri)3
(40 µL, 0.162 mmol) was added. The reaciton mixture was agitated and kept for 24 h at –25°C.
The precipitated red crystals were separated from a mother liquor by decantation and dried in oil-
pump vacuum. The red-orange crystals were dissolved in toluene and kept for 24 h at room
temperature. The IR monitoring shows complete disappearance of the metal-carbonyl bands for
adduct Mn2c. The solution was evaporated to dryness. The residue was washed with pentane
and dried in oil-pump vacuum to yield 54 mg (75%) of complex Mn4c as a yellow powder.
Calculated for C21H26MnO5P, %: C, 56.77; H, 5.90. Found, %: C, 56.96; H, 5.97. IR (toluene),
ν/cm–1: 1980s, 1924s (CO). 1H NMR (C6D6), δ: 1.13 (d, 18H, 3JHH = 6.1 Hz, POCH(CH3)2), 4.41
(s, 5H, Cp), 4.67, 4.71 (2 m, 2H, CH(P)=CHPh), 4.82 (m, 2H, POCH(CH3)2), 6.91 (t, 2H, 3JHH
6.9 Hz, Hortho Ph), 6.95 (t, 1H, 3JHH = 6.9 Hz, Hpara Ph), 7.06 (dd, 2H, 3JHH = 7.3 Hz, Hmeta Ph).
31P{1H} NMR (C6D6), δ: 32.00 (P(O)(OPri)2).
=
Complex Mn2a on keeping in a toluene solution slowly (24 h) transforms into the corresponding
η2-phosphorylalkene complex Cp(CO)2Mn{PhCH=CHP(O)(OMe)2} (Mn4a). IR (toluene),
ν/cm–1: 1980s, 1924s. 31P{1H} NMR (C6D6), δ: 36.60 (P(O)(OCH3)2).
Complex Mn2b on keeping on a toluene solution (24 h) or as a dry powder in air slowly
transforms into the η2-phosphorylalkene complex Cp(CO)2Mn{PhCH=CHP(O)(OEt)2} (Mn4b).
IR (toluene), ν/cm–1: 1980s, 1924s. 31P{1H} (C6D6), δ: 33.65 (P(O)(OCH2CH3)2).
Complex Mn3 was found to be quite stable towards hydrolysis by water traces being present in
organic solvents and undergo no changes upon keeping in toluene for 2 h and acetonitrile for 20
min in a CaF2 cell, but upon dissolution in acetone it slowly (18 h in a CaF2 cell) transforms into
the corresponding η2-phosphorylalkene complex Cp(CO)2Mn{η2-PhCH=CHP(O)(Ph)OEt}
(Mn5). IR (acetone), ν/cm–1: 1980s, 1920s.
The rhenium η2-phosphorylalkene complexes can be obtained conveniently either by long-term
stirring a mixture of Re1 and a P–OR nucleophile in hexane (procedure I) or by dilution of a
stirred reaction solution with wet diethyl ether (procedure II).
18

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4.3.2. Cp(CO)2Re{η2-PhC2H=C1HP(O)(OEt)2} (Re5b)
I. To a solution of complex Re1 (20 mg, 0.049 mmol) in hexane (3 mL), P(OEt)3 (9 mg, 0.054
mmol) was added and the reaction mixture was stirred for 76 h. The light-beige precipitate was
filtered off and dried in air to yield 22 mg (80 %) of complex Re5b as off-white crystals.
II. A solution of complex Re1 (20 mg, 0.049 mmol) and P(OEt)3 (9 mg, 0.054 mmol) in dry
diethyl ether (1 ml) was stirred for 2.5 h. The reaction mixture was diluted with diethyl ether (2
mL). Degassed water (0.05 mL, 2.8 mmol) was added and the mixture was stirred for 24 h. The
resulting solution was passed through a silica gel pad (0.5 cm) and dried in vacuo to dryness. The
residue was recrystallized from hexane to yield 20 mg (72%) of complex Re5b as off-white
needle crystals. Calculated for C19H22O5PRe, %: C, 41.68; H, 4.05. Found, %: C, 41.60; H, 4.01.
1
IR (hexane), ν/cm–1: 1996s, 1926s (CO). H NMR (C6D6), δ: 1.08 (t, 3H, OCH2CH3, 3JHH = 7.1
3
3
2
Hz), 1.27 (t, 3H, POCH2CH3, JHH = 7.1 Hz), 3.15 (dd, 1H, JHH = 10.9 Hz, JPH = 2.8 Hz,
=CHP), 4.03 (m, 2H, POCH2CH3), 4.16 (dq, 2H, OCH2CH3), 4.58 (dd, 1H, 3JHH = 10.9 Hz, 3JPH
= 17.8 Hz, =CHPh), 5.00 (s, 5H, Cp), 6.97-7.36 (m, 5H, Hortho, Hmeta and Hpara Ph). 31P{H} NMR
13
3
(C6D6), δ: 35.0 (P(O)(OEt)2). C{H} NMR (C6D6), δ: 16.38 (d, JCP = 5.7 Hz, POCH2CH3),
16.60 (d, 3JCP = 6.4 Hz, POCH2CH3), 21.33 (d, 1JCP = 179.8 Hz, =CHP), 35.67 (d, 2JCP = 4.9 Hz,
2
2
=CHPh), 61.38 (d, JCP = 7.1 Hz, POCH2CH3), 61.60 (d, JCP = 5.7 Hz, POCH2CH3), 87.95 (s,
3
Cp), 125.85 (s, Cpara Ph), 125.94 (s, Cmeta Ph), 128.67 (s, Cortho Ph), 145.89 (d, JCP = 7.8 Hz,
Cipso Ph), 199.85 (s, CO), 203.21 (s, CO).
4.3.3. Cp(CO)2Re{η2-PhC2H=C1HP(O)(OPri)2} (Re5с)
To a solution of complex Re1 (20 mg, 0.049 mmol) in hexane (3 mL), P(OPri)3 (12 µL, 0.049
mmol) was added and the reaction mixture was stirred for 65 h at room temperature. The light-
beige precipitate formed was filtered off and dried in air to yield 23 mg (85%) of complex Re5c
as off-white crystals. Calculated for C21H26O5PRe, %: C, 43.82; H, 4.55. Found: C, 44.03; H,
1
3
4.54. IR (hexane), ν/cm–1: 1995s, 1930s (CO). H NMR (C6D6), δ: 1.13 (d, 3H, JHH = 6.1 Hz,
3
3
POCHCH3), 1.27 (d, 3H, JHH = 6.2 Hz, POCHCH3), 1.37 (d, 3H, JHH = 6.1 Hz, POCHCH3),
3
3
2
1.38 (d, 3H, JHH = 6.1 Hz, POCHCH3), 3.18 (dd, 1H, JHH = 11.0 Hz, JPH = 2.1 Hz, =CHP),
3
3
4.58 (dd, 1H, JHH = 11.0 Hz, JPH = 17.9 Hz, =CHPh), 4.79 (m, 2H, PCH(CH3)2), 5.04 (s, 5H,
Cp), 7.00 (t, 3JHH = 7.3 Hz, Hpara Ph), 7.03 (d, 3JHH = 7.0 Hz, Hortho Ph), 7.20 (dd, 3JHH = 7.7 Hz,
Hmeta Ph). 13C{H} NMR (C6D6), δ: 23.01 (d, 4JCP = 4.9 Hz, POCH(CH3)2), 23.08 (d, 1JCP = 180.9
4
4
Hz, =CHP), 23.79 (d, JCP = 4.2 Hz, POCH(CH3)2), 24.09 (d, JCP = 3.8 Hz, POCH(CH3)2),
24.33 (d, 4JCP = 4.2 Hz, POCH(CH3)2), 35.45 (d, 2JCP = 5.7 Hz, =CHPh), 69.42 (d, 3JCP = 7.2 Hz,
POCH(CH3)2), 69.87 (d, 3JCP = 5.3 Hz, POCH(CH3)2), 87.84 (s, Cp), 125.73 (s, Cpara Ph), 125.85
(s, Cmeta Ph), 128.65 (s, Cortho Ph), 146.00 (d, 3JCP = 7.9 Hz, Cipso Ph), 199.96 (s, CO), 203.09 (s,
CO). 31P{H} NMR (C6D6), δ: 32.5 (P(O)(OPr-i)2).
19

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4.3.4. Cp(CO)2Re{η2-PhC2H=C1HP(O)(OEt)Ph} (Re6)
A solution of complex Re1 (20 mg, 0.049 mmol) and PPh(OEt)2 (9.7 mg, 0.049 mmol) in dry
diethyl ether (1 mL) was stirred for 2.5 h. The reaction solution was diluted with diethyl ether (2
mL), degassed water (0.05 mL, 2.8 mmol) was added, and the mixture was stirred for 24 h. The
resulting solution was passed through a silica gel pad (0.5 cm) and evaporated to dryness in
vacuo. The residue was recrystallized from hexane to obtain 23 mg (82%) of complex Re6 as
off-white needle crystals. Calculated for C23H27O4PRe, %: C, 47.66; H, 3.83. Found, %: C,
47.85; H, 3.96. IR (toluene), cm–1: 1990s, 1920s (CO).
1
3
Major diastereomer of Re6. H NMR (C6D6), δ: 1.06 (t, 3H, JHH = 6.9 Hz, CH3), 3.24 (dd, 1H,
3JHH = 10.8 Hz, 2JPH = 4.3 Hz, =CHP), 4.01 (m, 2H, POCH2CH3), 4.82 (s, 5H, Cp), 4.85 (dd, 1H,
3
3JHH = 10.8 Hz, JPH = 16.0 Hz, =CHPh), 6.9–8.2 (m, 10 H, CHPh and PPh). 31Р{1H} NMR
(C6D6), δ: 43.0 (s, P(O)(OEt)Ph).
1
Minor diastereomer of Re6. H NMR (C6D6), δ: 0.90 (t, 3H, 3JHH = 7.0 Hz, CH3), 3.16 (dd, 1H,
3JHH = 11.2 Hz, 2JPH = 4.1 Hz, =CHP), 3.93 (m, 2H, POCH2CH3), 4.59 (dd, 1H, 3JHH = 11.2 Hz,
3JPH = 17.1 Hz, =CHPh), 5.16 (s, 5H, Cp), 6.9–8.2 (m, 10 H, CHPh and PPh). Р{1H} NMR
31
(C6D6), δ: 42.6 (s, P(O)(OEt)Ph).
The ratio of major to minor diastereomers was about 70 : 30.
4.3.5. Cp(CO)2Re{η2-PhC2H=C1HP(O)Ph2} (Re7)
To a solution of complex Re4 (20 mg, 0.031 mmol) in benzene (3 mL), degassed water (0.5 mL,
2.8 mmol) was added and the mixture was stirred for 24 h at room temperature. The resulting
solution was passed through a silica gel pad (0.5 cm) and evaporated to dryness in vacuo. The
residue was recrystallized from hexane to obtain 15.4 mg (81%) of complex Re7 as white needle
crystals.
16
3
IR (toluene), ν/cm–1: 1990s, 1920s (CO), 1176s (P= O). 1H NMR (C6D6), δ: 3.64 (dd, 1H, JHH
2
3
3
= 11.1 Hz, JPH = 14.3 Hz, =CHP(O)), 4.87 (dd, 1H, JHH = 11.1 Hz, JPH = 15.6 Hz, =CHPh),
13
1
5.02 (s, 5H, Cp), 6.97-8.13 (m, 15H, =CHPh, PPh2). C{H} NMR (C6D6), δ: 27.45 (d, JCP
=
90.6 Hz, =CHP), 33.66 (s, =C2HPh), 87.33 (s, Cp), 131.44–125.83 (six s, Cortho, Cmeta, and Cpara
1
1
of =CHPh and PPh), 135.71 (d, JCP = 103.5 Hz, Cipso PPh), 138.23 (d, JCP = 96.7 Hz, Cipso
3
31
PPh), 146.05 (d, JCP = 5.3 Hz, Cipso =CHPh), 200.30 (s, CO), 203.44 (s, CO). P{H} NMR
(C6D6), δ: 33.8 (P(O)Ph2).
4.3.6. Cp(CO)2Re{η2-PhC2H=C1DP(O)Ph2} (d1-Re7)
Complex Re4 (18 mg, 0.028 mmol) was dissolved in a mixture of benzene (2 mL) with D2O (30
mg, 1.498 mmol). The course of the reaction was monitored by IR spectroscopy, which showed
complete disappearance of the initial complex with νCO 1890s, 1824s cm–1 within 7 h being
20

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accompanied by the appearance of new bands with νCO 1990s, 1920s cm–1. The mixture was
stirred overnight. The benzene layer was separated from the excess of D2O using a Pasteur
pipette, passed through a silica gel pad (2 cm), and evaporated to dryness. The residue was
washed with hexane (2 × 0.5 mL) and dried in vacuo to yield 16 mg (93%) of the target product
d1-Re7 (according to the 1H NMR spectrum, the D/H ratio was 65:35).
16
1
IR (benzene), ν/cm–1: 1990s, 1920s (CO), 1177s (P= O). H NMR (C6D6), δ: 3.65 (dd, 0.35H,
3JHH = 11.1 Hz, 2JPH = 14.5 Hz, =CHP(O)), 4.84, 4.89 (2 m, 1H, 3JHH = 11.1 Hz, 3JPH = 14.5 Hz,
=CHPh), 5.02 (s, 5H, Cp), 6.97-7.32 (m, 11H, =CHPh, Hmeta and Hpara from PPh2), 7.88 (br.m,
2H, Hortho PPh2), 8.13 (dd, 2H, 3JHH = 8.0 Hz, 3JHP = 9.8 Hz, Hortho PPh2).
4.3.7. Cp(CO)2Re{η2-PhC2H=C1HP(18O)Ph2} (18O-Re7)
18
Complex Re4 (18 mg, 0.028 mmol) was dissolved in a mixture of benzene (2 mL) with H2 O
(30 mg, 1.499 mmol). The reaction mixture was stirred for 7 h. The benzene layer was separated
18
from the excess of H2 O using a Pasteur pipette, passed through a silica gel pad (2 cm), and
evaporated to dryness. The residue was washed with hexane (2 × 0.5 mL) and dried in vacuo to
18
18
yield 15 mg (87%) of the target product O-Re7 (the IR spectrum shows that the O/16O ratio
was about 60:40, which follows from the intensity ratio between νP= (1147 cm–1) and νP=
18
16
O
O
(1178 cm–1)). IR (benzene), ν/cm–1: 1990s, 1920s (CO), 1178m (P=16O), 1147m (P=18O).
4.3.8. Cp(CO)2Re{η2-PhC2H=C1HP(O)(OPh)2} (Re9)
A solution of complex Re1 (20 mg, 0.049 mmol) and P(OPh)3 (17 mg, 0.055 mmol) in hexane (3
mL) was refluxed with stirring for 36 h. The solution was cooled to –25 °C and kept for 2 h at
this temperature. The light-beige precipitate that formed was separated from a mother liquor by
decantation, washed with cold hexane (3 × 0.5 mL), and dried in water-pump vacuum to yield 16
mg (50%) of complex Re9 as off-white crystals. Calculated for C27H22O5PRe, %: C, 50.39; H,
3.45. Found, %: C, 50.45; H, 3.51. IR (hexane), ν/cm-1: 2000s, 1931s (CO). 1H NMR (C6D6), δ:
2
3
3
3
3.37 (dd, 1H, JPH = 3.5 Hz, JHH = 10.9 Hz, =CHP), 4.45 (dd, 1H, JPH = 19.0 Hz, JHH = 10.9
Hz, =CHPh), 4.85 (сs, 5H, Cp), 6.78-7.22 (m, 13H, OPh, Hmeta and Hpara from =CHPh), 7.68 (d,
2H, 3JHH = 8.6 Hz, Hortho =CHPh). 31Р{1H} NMR (C6D6), δ: 29.6 (P(O)(OPh)2).
Acknowledgments
This work was financially supported by the Russian Foundation for Basic Research (Project No.
15-03-04745), the Presidium of the Russian Academy of Sciences (Program P-8 “Development
of organic synthesis methodology and design of compounds with valuable applied properties”),
and the Ministry of Education and Science of the Russian Federation (Agreement No.
21

ACCEPTED MANUSCRIPT
02.a03.21.0008). The contribution of the Center for molecule composition studies of INEOS
RAS is gratefully acknowledged.
Appendix. Supplementary data
CCDC 1569069, 1569070, 1569067, and 1569068 contain the crystallographic data for
compounds Mn2b, Re2a, Re2b, and Re5a, respectively. These data can be obtained free of
charge
from
the
Cambridge
Crystallographic
Data
Center
via
http://www.ccdc.cam.ac.uk/conts/retrieving.html. The corresponding CIF files are attached to
Supporting Information.
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26

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► P–OR nucleophiles add to the Cα atom of Mn and Re vinylidenes to afford zwitter-ionic
adducts Cp(CO)M¯ –C(+P(OR)R'2)=C(H)Ph.
► The Mn adducts are very sensitive to water traces, but can be isolated by low-temperature
crystallization.
► The Re adducts slowly react with added water to give phosphorylalkenes Cp(CO)2Re{η2-E-
HC[P(O)R'2]=C(H)Ph}.
► Isotopic experiments showed the hydrolysis of quasiphosphonium adducts to include the P–O
bond cleavage and binding of the water hydrogen to the C atom bearing the >P=O group.