Reactions of Manganese and Rhenium Vinylidene Complexes with Hydrophosphoryl Compounds

Article abstract of DOI:10.1021/acs.organomet.6b00626

We studied the reactions of manganese and rhenium phenylvinylidenes Cp(CO)₂MCC(H)Ph (Mn1 M = Mn; Re1 M = Re) with HP(O)R₂ (R = C₆F₅, Ph, and OEt) and HP(S)Ph₂, which resulted in the selective formation of η²-E-phosphorylalkene complexes Cp(CO)₂M{η²-E-H[R₂(O)P]CC(H)Ph} (Mn2, Re2 R = C₆F₅; Mn3, Re3 R = Ph; and Mn6, Re6 R = OEt) and Cp(CO)₂M{η²-E-H[Ph₂(S)P]CC(H)Ph} (Mn5, Re5). The DFT/B3LYP(6-31G*) analysis showed the model reactions of Mn1 with HP(O)Me₂ and HP(O) (OMe)₂ to proceed via the initial transition state Cp(CO)₂{Ph(H)CC}Mn···HO-PR₂ (TS1) where the minor PA form HO-PR₂ is hydrogen-bonded to the metal, followed by stereoselective (trans- to the phenyl group) addition of the PA phosphorus atom to the C_α-vinylidene atom, which defines both the rate of the process and the anti-Markovnikov structure of the reaction product. The reactions can proceed at a relatively low content of the reactive PA form.

Full text of DOI:10.1021/acs.organomet.6b00626

Article
pubs.acs.org/Organometallics
Reactions of Manganese and Rhenium Vinylidene Complexes with
Hydrophosphoryl Compounds
Kamil I. Utegenov,† Vasilii V. Krivykh,† Andrei M. Mazhuga,† Oleg S. Chudin,‡
Aleksander F. Smol’yakov,† Fedor M. Dolgushin,† Evgenii I. Goryunov,† and Nikolai A. Ustynyuk*,†
†A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow 119991, Russian
Federation
‡Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences, ul. K. Marksa 42,
Krasnoyarsk 660049, Russian Federation
S
* Supporting Information
ABSTRACT: We studied the reactions of manganese and rhenium phenylvinylidenes
Cp(CO)2MCC(H)Ph (Mn1 M = Mn; Re1 M = Re) with HP(O)R2 (R = C6F5, Ph,
and OEt) and HP(S)Ph2, which resulted in the selective formation of η2-E-
phosphorylalkene complexes Cp(CO)2M{η2-E-H[R2(O)P]CC(H)Ph} (Mn2, Re2 R =
C6F5; Mn3, Re3 R = Ph; and Mn6, Re6 R = OEt) and Cp(CO)2M{η2-E-H[Ph2(S)P]C
C(H)Ph} (Mn5, Re5). The DFT/B3LYP(6-31G*) analysis showed the model reactions of Mn1 with HP(O)Me2 and HP(O)
(OMe)2 to proceed via the initial transition state Cp(CO)2{Ph(H)CC}Mn···HO−PR2 (TS1) where the minor PA form
HO−PR2 is hydrogen-bonded to the metal, followed by stereoselective (trans- to the phenyl group) addition of the PA
phosphorus atom to the Cα-vinylidene atom, which defines both the rate of the process and the anti-Markovnikov structure of
the reaction product. The reactions can proceed at a relatively low content of the reactive PA form.
the oxygen and phosphorus atoms within dimer associates.3
Due to a “latent” presence of PA forms, HPCs both react with
INTRODUCTION
■
Although tautomeric hydrophosphoryl compounds (HPCs)
organic substrates (hydrophosphorylation of compounds with
exist predominantly as the P(V) forms HP(O)R2 (hereinafter
polar carbon−carbon and carbon-heteroatom multiple bonds,
referred to as PO forms, R = alkyl, aryl, or alkoxyl), their
reactivities are defined mainly by the minor nucleophilic P(III)
forms HO−PR2 (hereinafter, PA forms; Scheme 1).
addition of sulfur, etc.)4 and form complexes with transition
metals.5−8 In recent years, the interest in hydroxyphosphine
and dialkyl phosphite complexes (PA)M increased significantly
thanks to their efficient catalytic applications.9,10 Coordination
Scheme 1
of a HPC to a transition metal shifts the tautomeric equilibrium
in favor of the minor PA form. The analogous shift of the
tautomeric equilibrium may be expected also upon nucleophilic
addition of HPCs to the MC bonds of transition metal
cumulene complexes; however, such reactions have not been
studied until now.11 Since the electrophilic Cα atom in the
A considerable content of the PA form is typical of
compounds with electron-withdrawing substituents at the
phosphorus atom; the existence of single PA tautomer in
dilute solutions was noted only for (CF3)2P−OH and
(C2F5)2P−OH.1a,b The presence of both tautomers was
observed for a series of HPCs based on the 31P NMR data
manganese and rhenium vinylidenes Cp(CO)2MCC(H)-
Ph (hereinafter, Mn1 M = Mn, Re1 M = Re) is well-known to
add phosphines and phosphites,12 it was interesting to study
whether these complexes can add HPCs. In the present work,
we studied the reactions of manganese Mn1 and rhenium Re1
vinylidenes with secondary phosphine oxides HP(O)Ph2 and
HP(O)(C6F5)2, diphenylphosphine sulfide HP(S)Ph2, and
diethyl phosphite HP(O)(OEt)2, which are shown to afford
selectively η2-E-phosphorylalkenes Cp(CO)2M{η2-Ph(H)C
CHP(E)R2} (M = Mn and Re; E = O and S; R = C6F5, Ph, and
OEt). The reactions of Mn1 with HP(O)Me2 and HP(O)-
(OMe)2 were examined theoretically, which allowed revealing
the reaction pathway where the initial nucleophilic PA addition
and DFT estimations of the relative energies of tautomers, for
1a,c−e
example, HP(O)R2 with R = C6F5,
C5F4N,1f t-Bu,1d Ph,1f
p-Tol,1f p-C6H4F,1f and 3,5-(CF3)2C6H3.1f The tautomeric
equilibrium was observed also for the HPCs of cyclic
structure.1h,i Even if the content of PA is insufficient for a
reliable identification by 31P NMR spectroscopy, its “latent”
presence in solution follows from indirect signs, for example,
1d
1
from the temperature dependence of JPH
.
Although
tautomerization via the intramolecular 1,2-P,O-hydrogen shift
is forbidden by the energy barrier (50−60 kcal/mol),2 the PA
and PO forms can be interconverted reversibly even at room
temperature due to synchronous hydrogen migration between
Received: August 3, 2016
© XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.6b00626
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Article
to the Cα atom is the rate-limiting step and defines the product
geometry.
reaction of Re1 does not proceed in THF at room temperature
but proceeds smoothly in refluxing THF to yield the rhenium
analog Re2 (Scheme 2). Complexes Mn2 and Re2 were
1
characterized by IR, H, 13C, 19F, and 31P NMR spectroscopy
RESULTS AND DISCUSSION
■
and the molecular geometry of Re2 was established by X-ray
diffraction (Figure 1 and Table S1).
Reactions of Mn1 and Re1 with Secondary Phosphine
Oxides. A priori one can expect Mn1 and Re1 to react only
with the PA form, and the rate of these reactions to be defined
primarily by the content of this form. A relatively high content
of the PA form is typical of HP(O)(C6F5)2. According to the
DFT calculations, the PA form is 1.7 kJ/mol1a more stable than
the PO one, and its content in solution as for other PA forms is
defined by associative interactions with a solvent. In oxygen-
containing solvents, the PA content is quite high (18%1a in
methanol, 43%1a in dimethoxyethane, 601a and 71%1e in diethyl
ether, 55%1a in THF, and 76%1a in DMSO). At the same time,
the 31P NMR spectra of HP(O)(C6F5)2 in toluene, dichloro-
methane, acetonitrile, carbon tetrachloride, C6D6, and CD3NO2
show the PO form to be the only one in solution.1a,d,e For this
reason, Et2O and THF seemed to be optimum solvents for the
reactions with HP(O)R2, especially, in the cases when there are
no reliable data on the content of tautomeric PA form (e.g.,
HP(S)Ph2 and HP(O)(OEt)2).
Figure 1. Molecular structure of Cp(CO)2Re{η2-Ph(H)CC(H)P-
(O)(C6F5)2} (Re2). Selected bond lengths (Å): Re1−C6 2.2237(14),
Re1−C7 2.2442(13), Re1−C14 1.9049(15), Re1−C15 1.9185(16),
P1−O3 1.4772(11), P1−C6 1.7764(14), C6−C7 1.441(2), Re1−X1
1.961(2) (X1 is the centroid of the Cp ring); selected torsion angles
(deg): P1−C6−C7−C8−133.35(12); X1−Re1−C6−P1−31.8(2),
X1−Re1−C7−C8 121.5(2).
The reaction between Mn1 and HP(O)(C6F5)2 proceeds in
THF at room temperature to afford η2-E-phosphinylstyrene
complex Cp(CO)2Mn{η2-Ph(H)CC(H)P(O)(C6F5)2}
(Mn2) in yield of 74% (Scheme 2 and Table 1). The same
Scheme 2
As for HP(O)Ph2, DFT calculations show the PO form to be
by 12.64 kJ/mol (enthalpy) more stable than the PA one
whose portion should be only 0.73% in the absence of
associative interactions.1d Nevertheless, the reactions of Mn1
and Re1 with diphenylphosphine oxide in Et2O and THF also
afford η2-E-phosphinylstyrene complexes Cp(CO)2M{η2-Ph-
Table 1. Experimental Details for the Reactions of Mn1 and Re1 with HP(E)R2
run
HP(E)R2
comp.
solv.
time, t
product
base
1
Mn1
Re1
Re1
Mn9
Mn1
Mn1
Mn1
Re1
Re1
Re1
Re1
Mn1
Re1
Re1
Re1
Re1
Mn1
Mn1
Re1
Re1
Re1
Re1
Mn1
Re1
THF
THF
THF
Et2O
THF
THF
Et2O
THF
THF
Et2O
Et2O
THF
C6H6
C6H6
THF
THF
THF
Et2O
THF
THF
THF
Et2O
THF
THF
20 °C, τ1/2 = 17 min, 4 h for complete reaction
20 °C, 2 h
66 °C, 4 h
20 °C, 120 h
20 °C, τ1/2 = 170 min, 20 h for complete reaction
20 °C, τ1/2 = 147 min, cmax after 6 h
20 °C, 3 h
20 °C, 1 h
Mn2 (74%)
no reaction
Re2 (75%)
2
HP(O)(C6F5)2
3
4
(C6F5)2P(O)CH(Ph)CH2P(O)(C6F5)2
5
Mn3 (37.5%) + Ph2P(O)CH(Ph)CH2P(O)Ph2
6
Mn3 + Ph2P(O)CH(Ph)CH2P(O)Ph2 (17%)
Et3N
7
Mn3 (79%) + Ph2P(O)CH(Ph)CH2P(O)Ph2
8
HP(O)Ph2
no reaction
9
66 °C, 6 h
20 °C, 22 h
35 °C, 2 h
Re3 (59%) and Ph2P(O)CH(Ph)CH2P(O)Ph2
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
no reaction
Re3 (85%)
20 °C, τ1/2 = 26 min, max. product conc. after 2 h
20 °C, 24 h
20 °C, τ1/2 = 6 h, 48 h for complete reaction
66 °C, 1 h
66 °C, 15 h
(1) r.t.; (2) HBF4·OEt2; −60 °C → r.t.
20 °C, 44 h
66 °C, 3 h
66 °C, 17 h
66 °C, 1 h
Mn5
Et3N
Et3N
no reaction
HP(S)Ph2
Re5 (93%)
no reaction
Re5 (89%)
Et3N
LiSP(Ph)2
Mn5 (47%)
LiOt-Bu
Mn6 (51%)
no reaction
Et3N
HP(O)(OEt)2
no reaction
(CH2)6N4
K2CO3
no reaction
35 °C, 48 h
20 °C, instantly
(1) 20 °C; (2) −60 °C → 20 °C
no reaction
LiOP(OEt)2
LiOP(OEt)2
Mn7 + NH4Cl(aq) → Mn6 (66%)
Re7 + HBF4·OEt2 → Re6 (56%)
LiOt-Bu
LiOt-Bu
B
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(H)CC(H)P(O)Ph2} (Mn3 M = Mn and Re3 M = Re)
preparation of Mn5 (Scheme 5) via the reaction with LiSPPh2
obtained by deprotonation of HP(S)Ph2 with t-BuOLi to form
(Scheme 3), but they proceed slower than those with
Scheme 3
Scheme 5
a presumable anionic complex Li[Cp(CO)2Mn−−C(P(S)-
Ph2)CHPh] (Mn4) and subsequent protonation of Mn4
with HBF4·OEt2 to yield the target Mn5. The latter step is
likely to proceed analogously to that of Mn7 (see Scheme 8
below).
Neither does the rhenium vinylidene Re1 react with
diphenylphosphine sulfide in benzene in the absence of base.
The addition of triethylamine to a benzene solution of the
reaction mixture at room temperature induces a slow reaction
(τ1/2 ≈ 5 h, the complete transformation requires ∼48 h) to
afford a η2-E-thiophosphinylstyrene complex Cp(CO)2Re{η2-E-
PhHCCHP(S)(Ph)2} (Re5). Upon refluxing a mixture of
Re1 and HP(S)Ph2 in THF in the presence of Et3N, the
reaction proceeds faster (Scheme 6). The structure of Re5 was
confirmed additionally by X-ray diffraction (see Figure 2 and
Table S1).
HP(O)(C6F5)2 (Table 1). The reaction between Mn1 and
HP(O)Ph2 in THF at room temperature is not selective: Along
with the target product Mn3, unidentified manganese
complexes and Ph2P(O)CH(Ph)CH2P(O)Ph2 (up to 20%)
are produced. Presumably, the diphosphine dioxide results from
the double addition of HP(O)Ph2 which is in excess to Mn3
due to a low rate of its formation in the initial step. An attempt
to accelerate the formation of Mn3 in the presence of
triethylamine and thereby to decrease the amount of the
diphosphine dioxide failed: In this case it was also the main
isolated product (yield of 17%). We succeeded in diminishing
the side reaction using diethyl ether as the reaction medium. In
this solvent, Mn3 was obtained in higher yield of 78%; this is
likely due to a poor solubility of Mn3 in Et2O, which allows for
withdrawal of it from the secondary reaction (in this case the
diphosphine dioxide is produced in slight amounts). Complex
Re1 does not react with HP(O)Ph2 either in diethyl ether or
THF at room temperature, but reacts in these solvents upon
reflux; the yield of Re3 in Et2O is higher than that in THF.
The reactions with phosphine oxides were assumed to
proceed according to Scheme 4 via the following steps: (a) the
Scheme 6
Scheme 4
“external” nucleophilic addition of HPC to form adduct A
where the metal is hydrogen-bonded to the OH hydrogen; (b)
hydrogen migration to the metal atom; and (c) C,H-reductive
elimination in hydride B to rearrange into the reaction product
C. We consider only the trans-addition of the PA form with
regard to the Ph group, since earlier12j we have found exactly
trans-addition of tertiary phosphines to Mn1 and Re1.
Intermediates A and B, which cannot be detected by IR and
NMR spectroscopy, were identified on the potential energy
surface upon theoretical study of the reactions of Mn1 with
HO−PMe2 and HO−P(OMe)2 (see below).
Reactions of Mn1 and Re1 with Diphenylphosphine
Sulfide. In the absence of base, Mn1 reacts with HP(S)Ph2 in
THF very slowly without forming the olefin complex
Cp(CO)2Mn{η2-E-PhHCCHP(S)(Ph)2} (Mn5). However,
the addition of base (Et3N) accelerates the reaction initially
resulting in a rapid (τ1/2 ≈ 26 min) formation of Mn5, which
upon long-term stirring in THF undergoes subsequent
transformation into an unknown green product. We attempted
to obtain a pure Mn5 using a two-step procedure for the
Figure 2. Molecular structure of Cp(CO)2Re(η2-PhCHCHP(S)-
Ph2) (Re5). Selected bond lengths (Å): Re1−C6 2.210(3), Re1−C7
2.257(3), Re1−C14 1.907(3), Re1−C15 1.921(3), P1−S1 1.9678(10),
P1−C6 1.793(3), C6−C7 1.438(3), Re1−X1 1.956(3) (X1 is the
centroid of the Cp ring); selected torsion angles (deg): P1−C6−C7−
C8−135.8(2); X1−Re1−C6−P1 136.2(3), X1−Re1−C7−C8−
26.6(3).
C
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There are literature data on the structure of the closest
analog of Re2 and Re5, Cp(CO)2Mn[PhCHCHP(O)-
(OEt)2].12e In all structures, the substituents at the olefin
ligand are in trans-disposition. The orientation of the
Cp(CO)2Mn fragment relative to the olefin coincides with
that of the Cp(CO)2Re fragment in the structure of Re2. In the
structure of Re5, this fragment is rotated by about 180° relative
to the axis passing through the Re atom and the center of the
olefin bond. One can note that the η2-coordinated double bond
in the structures of Re2 and Re5 (1.441(2) and 1.438(3) Å,
respectively) is elongated noticeably compared to that in the
Mn analog (1.395(8) Å), which is explained by a higher back-
donation from the rhenium atom. It is important to note that
the significant difference in the electronic properties of
substituents at the phosphorus atom in the structures of Re2
and Re5 has no effect on the olefin bond length and the
characteristics of η2-coordination to the rhenium atom (the
distance Re(1)−centroid(CC) is 2.115 Å in both com-
plexes).
protonation (Scheme 8) and the reaction of Mn1 with neutral
diethyl phosphite (Scheme 7) afford the same stereochemical
result (i.e., the formation of E-η2-phosphorylstyrene complex
Mn6). This suggests that the reaction of Mn1 with the neutral
diethyl phosphite also proceeds via an intermediate hydride
Mn8 corresponding to intermediate B in Scheme 4.
Theoretical Analysis of the Reactions between Mn1
and HP(O)R2 (R = Me and OMe). During the reactions of
Mn1 and Re1 with HPCs, the IR spectra of reaction mixtures
display a gradual decrease in the νCO band intensities of the
starting complexes Mn1 and Re1 and an increase in the νCO
band intensities of the reaction products, viz., η2-phosphoryl- or
phosphinylolefin complexes, with no νCO bands of intermedi-
ates being observed. For this reason, a deeper insight into the
regularities of these reactions could be provided only by their
theoretical study. Therefore, we studied the reactions of Mn1
with dimethylphosphine oxide HP(O)Me2 and dimethyl
phosphite HP(O)(OMe)2 by DFT (B3LYP/6-31G*). The
study showed the reactions to proceed in agreement with
Scheme 4 (with regard to some differences, see below); all
stationary points corresponding to intermediates and transition
states were identified on the potential energy surface. The
course of the reaction between Mn1 and HP(O)Me2 was
analyzed at 298.15 K for the gas phase and the diethyl ether
medium, while the reaction between Mn1 and HP(O)(OMe)2
was studied only for the gas phase. Since the data obtained were
found to be very similar in all cases under study, Scheme 9
Reactions of Mn1 and Re1 with Diethyl Phosphite.
Complex Mn1 reacts slowly (44 h) with HP(O)(OEt)2 in
diethyl ether at room temperature to afford Cp(CO)2Mn{η2-E-
PhHCCHP(O)(OEt)2} (Mn6) in yield of 51% (Scheme 7).
1
Along with H and 31P NMR characterization, the structure of
Mn6 was additionally confirmed by 13C NMR and 2D NMR
spectroscopy (see Figure S2).
Scheme 7
Scheme 9
Phosphorylstyrene complex Mn6 was also obtained upon
sequential treatment of Mn1 with the lithium salt Li[OP-
(OEt)2]13 and an aqueous solution of NH4Cl. The rhenium
analog Re1 does not react with neutral diethyl phosphite under
any conditions (reflux in THF or diethyl ether in the presence
of different-strength bases, Table 1, runs 19−22), but,
analogously to Mn1, reacts with the deprotonated diethyl
phosphite to produce the η2-phosphorylstyrene complex Re6
after protonation of the intermediate anion Re7 with HBF4·
OEt2 (Scheme 8).
Protonation of the metalate anions Mn7 and Re7 proceeds
analogously to that of the structurally close phosphoniostyryl
zwitter-ions [Cp(CO)2M−−C(+PR3)CHPh] (M = Mn and
Re).12j Of crucial importance is that the reaction of Mn1 with
lithium diethyl phosphite Li[O−P(OEt)2] followed by
shows only the course of the reaction between Mn1 and
HP(O)Me2 and Figure 4 reveals the energy profile of the same
reaction in the gas phase (with regard to the reaction between
Mn1 and HP(O)(OMe), see Scheme S1, Figure S1, and Tables
S3 and S4).
The reaction Mn1 + HP(O)Me2 → IV is exothermic: ΔG =
−49.07 kJ/mol and ΔH = −122.14 kJ/mol. A key step of the
process is the initial nucleophilic addition of the PA form to the
Scheme 8. Treatment of Mn6, Re6 from Mn1, Re1 and
a
Li[OP(OEt)2]
a
(i) LiOP(OEt)2, THF, 20 °C; (ii) M = Mn, H2O, and NH4Cl(aq), 12
Figure 3. Transition state (TS1 in Scheme 9) preceding the adduct
Cp(CO)2Mn−−C(+P(OH)Me2)CHPh (I).
h; M = Re and HBF4·OEt2, −60 °C → 20 °C.
D
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are light-yellow solids decomposing slowly in solution, and
complexes Re2, Re3, Re5, and Re6 are white solids with a
prominently higher stability. All complexes were characterized
1
by IR, H and 31P NMR spectroscopy, and in some cases by
19F, 13C NMR, and 2D NMR spectroscopy.
For the reactions under study, we can note general
regularities as follows: (1) The reactions proceed via stereo-
selective (trans to the phenyl group) addition of the PA form,
which is additionally favored by the presence of M···H−O−PR2
hydrogen bonding as shown in Figure 3 (or M···H−S−PR2 by
analogy). Contrary to expectations, this hydrogen bonding
precedes the Cα−P bond formation.14 (2) Due to a higher
electrophilicity of the Cα atom in Mn1, it always reacts faster
than the rhenium analog Re1. A higher rate of the reaction
between the hydrophosphoryl P(III) form and vinylidene
complex Mn1 compared to that of Re1 was predicted by us a
priori, since we have observed the same regularity for the
reaction of Mn1 and Re1 with tertiary phosphines.12j This
prediction15 was confirmed during this experimental study. (3)
The effect of base on the rate of reaction under study depends
both on the acidity of HP(E)R2 and on the base strength.
Triethylamine considerably accelerates the reaction between
Mn1 or Re1 and Ph2P(S)H and exhibits a slight effect in the
reaction between Mn1 and Ph2P(O)H, since favoring proton
transport between the phosphorus and oxygen atoms, it
increases to a certain extent the portion of the PA form. In
the cases when triethylamine or other medium-strength bases
cannot induce the reaction (for example, between Re1 and
HP(O)(OEt)2), one can use much stronger bases, such as t-
BuOLi, capable of deprotonating an HPC to form Li(O-PR2)
which reacts instantly with Mn1 or Re1 to form the anionic
adduct Mn7 or Re7. The anionic complexes are transformed
into the target product by protonation (Scheme 8). (4) The
ease of reactions with HPCs changes in the following order:
HP(O)(C6F5)2 > HP(O)Ph2 > HP(O)(OEt)2, and the
hydrothiophosphinyl compound HP(S)Ph2 is the least reactive
in the absence of base but becomes more reactive than its
oxygen analog in the presence of Et3N. The order given above
was suggested by the data from IR monitoring of the reaction
mixtures and has only a qualitative meaning.
Figure 4. Gibbs energy change during the reaction between Mn1 and
HP(O)Me2 in the gas phase (the values obtained in the diethyl ether
medium are given in parentheses).
α-carbon vinylidene atom to form adduct I. First, it is
characterized by the highest barrier (ΔG#= 100.81 kJ/mol)
and, therefore, defines the rate of the whole process. Second,
the structure of I determines the stereochemistry of the
phosphinylolefin IV, since the hydroxyphosphonium group in I
is in the trans-position with regard to the phenyl ring and the
subsequent reaction pathway, i.e. hydroxyl hydrogen transfer to
the metal followed by C,H-reductive elimination in the
intermediate hydride II, is already predetermined due to O−
H···Mn hydrogen bonding in I (the Mn···H distance is 2.628
Å).
O−H···Mn hydrogen bonding was unexpectedly found
already in the transition state (TS1) (Figure 3). The Mn···H
distance is 2.569 Å and the O−H−Mn angle is 148°, while the
Cα−P bond (the distance between the phosphorus and carbon
atoms is 2.554 Å) in TS1 has not formed. Although this step is
characterized by a negative enthalpy (−44.21 kJ/mol), the ΔG
value is found to be positive (19.86 kJ/mol) due to the decrease
in the entropy at this step.
At the next step, the hydroxyl hydrogen migrates to the
manganese atom to form the hydridostyryl derivative II where
the Mn−H bond length is 1.599 Å and the O···H distance
increased to 1.89 Å, which corresponds to the presence of P
O···H hydrogen bonding. This step is slightly endothermic
(ΔG = 38.47 kJ/mol and ΔH = 39.62 kJ/mol) and
characterized by a low activation barrier of ΔG# = 39.73 kJ/
mol.
The reductive elimination step II → III is very exothermic
(ΔG = −71.32 kJ/mol and ΔH = −66.47 kJ/mol), and its
activation barrier is low (ΔG# = 8.99 kJ/mol and ΔH# = 6.30
kJ/mol). The C−H bond in III (1.116 Å) is elongated due to
the agostic interaction with the metal atom. The final
exothermic transformation III → IV proceeds most rapidly
due to an insignificant activation barrier (ΔG# = 2.59 kJ/mol).
General Regularities of the Reactions of Mn1 and Re1
with HPCs. Table 1 gives experimental details for the reactions
of Mn1 and Re1 with secondary phosphine oxides,
diphenylphosphine sulfide, and diethyl phosphite under
different conditions. Complexes Mn2, Mn3, Mn5, and Mn6
Reaction between Phenylacetylene Complex Cp-
(CO)2Mn(η2-PhCCH) (Mn9) and HP(O)(C6F5)2. Although
addition of phosphorus nucleophiles PR3 to the alkyne ligand in
18e π-acetylene complexes [M](η2-RCCH) has been studied
̅
fragmentarily, the available data make it possible to assume with
certainty that the process will result in the formation of
corresponding E-β-phosphoniovinyl adducts [M]−−C(H)
C(+PR3)R or [M]−−C(R)C(+PR3)H rather than α-phos-
phoniovinyl ones [M]−−C(+PR3)C(H)R.16a−c We studied
the reaction of the phenylacetylene complex Cp(CO)2Mn(η2-
PhCCH) (Mn9) with bis-pentafluorophenylphosphine oxide
which in diethyl ether is known1e to contain 71% of the PA
form. Complex Mn9 was obtained in situ from the photo-
chemically generated ether complex Cp(CO)2Mn(OEt2) by the
reaction with phenylacetylene. While the vinylidene complex
Mn1 reacts rapidly with HP(O)(C6F5)2 at room temperature
(τ1/2 = 17 min in THF, Table 1, run 1), no signs of reaction are
observed in first hours after addition of HP(O)(C6F5)2 to a
solution of Mn9 in diethyl ether at room temperature. Only
after stirring overnight did a few of yellow crystals presumably
belonging to Mn2 appear on flask walls. Upon subsequent
stirring (for 5 days), the yellow crystals disappeared, and there
appeared a bulky white precipitate of (C6F5)2P(O)CH2CH-
E
DOI: 10.1021/acs.organomet.6b00626
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
1
(Ph)P(O)(C6F5)2 (41%) identified by H, 31P, and 19F NMR
spectroscopy. We assume the PA form (C6F5)2P−OH does not
add to the π-acetylene complex Mn9 due to an insufficient
electrophilicity of the alkyne ligand but adds to the vinylidene
complex Mn1 as far as it forms from Mn9 due to the acetylene-
vinylidene rearrangement17 (Scheme 10, the bottom part shows
Scheme 11
Scheme 10
M−H21 or M−P22 bonds followed by the C,P and C,H-
reductive elimination at the final step to afford the alkene
products D and E, respectively.23
In particular, this scheme does not consider in any way par-
ticipation of the PA form of HPC in the catalytic cycle.24
Moreover, possible proceeding of these processes via vi-
nylidene intermediates has not been considered, although, as
mentioned above, such “vinylidene path” is known for the
catalytic addition of nucleophiles to terminal alkynes.18 Based
on the data for hydrophosphorylation of the vinylidene
complexes Mn1 and Re1, one can propose an alternative
hypothetic Scheme 12 including alkyne coordination (step (a))
the proposed reaction pathway). In a special experiment, we
demonstrated that in the absence of phosphine oxide Mn9
slowly rearranges into Mn1 in diethyl ether (20 h at room
temperature). Due to a high excess of (C6F5)2P(OH) with
regard to the intermediately formed Mn2, there occurs a double
addition of the PA form to produce the diphosphine dioxide as
observed in the reaction between Mn1 and HP(O)Ph2
(Scheme 3). Compared to the π-alkyne isomers, the increased
ease of nucleophilic addition to vinylidene complexes forms the
basis for transition metal complex-catalyzed reactions of
terminal alkynes via vinylidene complexes as key intermedi-
ates.18
Scheme 12
Catalysis of Terminal Alkyne Hydrophosphorylation/
Hydrophosphinylation. From the data obtained in the
present work, one can emphasize three features directly
concerning the transition metal complex catalyzed hydro-
phosphorylation of terminal alkynes: (1) Hydrophosphoryla-
tion of vinylidenes Mn1 and Re1 proceeding via selective
nucleophilic addition of the PA form to the Cα-vinylidene atom
in the trans-position to the phenyl group (a rate-limiting step
which defines the reaction stereochemistry). (2) Hydrogen
bonding between the OH group of the PA form and the metal
atom, R2P−OH···[M] at the initial step. (3) Selective formation
of the anti-Markovnikov-type phosphorylstyrene complexes
[M]{η2-E-H(R2(O)P)CC(H)Ph}.
and subsequent acetylene-vinylidene rearrangement (step
(b)),25 the formation of the hydrogen-bonded complex F
(step (c)), nucleophilic addition of phosphorus to the
vinylidene Cα atom to form adduct G (step (d)), hydrogen
transfer to the metal atom to form the hydridophosphorylstyryl
compound H (step (e)), C,H-reductive elimination affording
the agostic complex I (step (f)), rearrangement of I to the
olefin complex J (step (g)), and final substitution of alkyne for
the phosphorylolefin ligand (step (h)).
It is noteworthy that the formation of hydrogen-bonded
complex between the PA form and Mn1, viz., Me2P−OH···
MnCC(H)Ph(CO)2Cp, in the transition state of hydro-
phosphorylation of the vinylidene complex (TS1 in Figure 3)
has not been proposed earlier. This bonding predetermines the
subsequent formation of Mn−H and Cα−P bonds (the
presence of lone-pair electrons on phosphorus provides an
easy nucleophilic addition of this atom to Cα, Scheme 12, step
(d)). Another coordination of HPC to the metal in the 18-
electron complex Mn1 seems to be unfavorable, because it will
afford complexes with more than 18-electron configuration.26
As applied to the manganese complexes under study ([M] =
Mn(CO)2Cp), this scheme is a model for the catalytic cycle
involving the corresponding 18-electron compounds. In this
Of doubtless interest is the question to which degree the
above-mentioned steps upon hydrophosphorylation of tran-
sition metal vinylidene complexes can be involved in the
catalytic cycles of transition-metal catalyzed hydrophosphor-
ylation of terminal alkynes. These reactions are being studied
intensively in the last 20 years in order to develop a selective
approach to alkenyl-substituted organophosphorus com-
pounds19 and typically afford either linear anti-Markovnikov20
(anti-M) E-1,2-adducts D (Scheme 11a) or branched
Markovnikov (M) 1,1-adducts E (Scheme 11b). The result of
the reaction depends on the type of HPC, catalyst, and
additives.
The mechanism of terminal alkyne hydrophosphorylation is
currently understudied. It is commonly assumed that the
catalytic cycles involve only the PO forms initially undergoing
oxidative addition at the P−H bond and alkyne insertion at the
F
DOI: 10.1021/acs.organomet.6b00626
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
4.02 (br.m, 1H, CHP(O)(C6F5)2), 4.74 (br.m, 1H, CHPh), 5.71
(s, 5H, Cp), 7.05 (m, 1H, p-C6H5), 7.25, 7.26 (2 br.s, 4H, o- and m-
C6H5). 13C{1H} NMR (acetone-d6, δ) 23.89 (s, CHP), 26.78 (s, 2C,
CH2 from 0.5THF), 32.90 (s, CHPh), 68.67 (s, 2C, O−CH2 from
0.5THF), 89.84 (s, Cp), 127.15, 127.26, 129.65 (s, C6F5), 138.10,
140.48, 144.08 (s, Ph), 146.8, 147.2, 149.7 (d, Ph), 199.72, 204.56 (s,
CO). 31P{1H} NMR (C6D6, δ) 16.57. 19F{1H} NMR (C6D6, δ)
case, the acetylene-vinylidene rearrangement proceeds by the
concerted mechanism and its barrier (114 kJ/mol) has been
determined for the close structural analog Cp(CO)2MnC
CH2.27 One can assume that the rates of acetylene-vinylidene
rearrangement and nucleophilic addition differ slightly. The
catalysis of terminal alkyne hydrophosphorylation by Scheme
12 seems to be possible and requires further studies.28
4
5
−161.6 (dm, 4F, JFP = 85.2 Hz, m-C6F5), −149.34 (dq, 2F, JFP
=
3
134.7 Hz, p-C6F5), −133.0 (dm, 4F, JFP = 629.6 Hz, o-C6F5).
CONCLUSIONS
Reaction between Cp(CO)2MnCCHPh (Mn1) and HP(O)-
(C6F5)2. A solution of Mn1 (100 mg, 0.359 mmol) and HP(O)(C6F5)2
(144 mg, 0.377 mmol) in THF (5 mL) was stirred for 4 h at room
temperature. IR monitoring shows the half-life of the starting
compound to be 17 min. The reaction mixture was concentrated,
and hexane (∼10 mL) was added. The precipitate formed was
separated by decantation and dried in vacuo to yield the olefin complex
Cp(CO)2Mn{η2-PhCHCHP(O)(C6F5)2} (Mn2) (174.5 mg, 74%)
as an amorphous yellow powder. IR (THF, ν, cm−1) 1982 (CO) s,
■
New reactions of manganese and rhenium phenylvinylidene
complexes Cp(CO)2MCC(H)Ph (Mn1 M = Mn; Re1 M
= Re) with hydrophosphoryl compounds HP(E)R2 (E = O, S)
resulting in the stereoselective formation of η2-E-phosphor-
ylalkene complexes Cp(CO)2M{η2-E-H[R2(E)P]CC(H)Ph}
have been studied. The DFT analysis showed the reactions to
proceed via initial formation of the complex Cp(CO)2{Ph(H)-
CC}Mn···HO-PR2, where the minor PA form HO-PR2 is
hydrogen-bonded to the metal, followed by stereoselective
addition of the PA form to the Cα vinylidene atom. It is a rate-
limiting step and defines the anti-Markovnikov structure of the
reaction product. The reactions can proceed also at a relatively
low content of the reactive PA form which is in the tautomeric
equilibrium with the PO form HP(O)R2 not involved in the
reaction. The reactions can be promoted by a base whose effect
depends on the HP(E)R2 acidity. The discovered trans-
formations can be applied to other HPCs and vinylidene
complexes of other transition metals, as well as to other proton-
containing heteroatomic nucleophiles. Possible mechanisms of
terminal alkyne hydrophosphorylation were discussed.
1
1928 (CO), 1644 (FCCF) w. H NMR (acetone-d6, δ) 4.5−5.3
(br.s, 7H, Cp signal overlaps with the signals for HCCH), 7.15 (t,
1H, p-C6H5), 7.30 (t, 2H, m-C6H5), 7.42 (br.m, 2H, o-C6H5). 31P{1H}
NMR (acetone-d6, δ) 17.36. 19F{1H} NMR (acetone-d6, δ) −103.37
(dm, 4F, 4JFP = 124 Hz, m-C6F5), −90.84 (dq, 2F, 5JFP = 222.9 Hz, p-
3
C6F5), −74.6 (dm, 4F, JFP = 388.6 Hz, o-C6F5).
Reaction between Re1 and HP(O)Ph2. A solution of Re1 (100
mg, 0.244 mmol) and HP(O)Ph2 (49.4 mg, 0.244 mmol) in Et2O (5
mL) was refluxed for 2 h (the color changed from orange to pale-
yellow and a slight precipitate formed; on cooling the solution became
thick). The mixture was evaporated to dryness, and the residue was
dissolved in toluene (1 mL) and chromatographed at low temperature
(below −20 °C) on a silica gel column (10 × 1 cm). The first yellow-
orange fraction of the remaining starting Re1 was eluted with pure
toluene. The second yellow fraction was eluted with acetone−toluene
(1:10). The third colorless fraction of the reaction product
Cp(CO)2Re{η2-PhCHCHP(O)Ph2} (Re3) was eluted with ace-
tone−toluene (1:5) and evaporated to dryness. The residue was
washed with pentane and dried in vacuo to yield Re3 (126.3 mg,
84.5%) as a grayish-white crystalline powder. Calculated for
C27H22O3PRe × 0.25C6H5CH3, %: C, 54.41; H, 3.81; P, 4.88.
Found, %: C, 54.67; H, 3.87; P, 5.08. IR (Et2O, ν, cm−1) 1984 (CO) s,
1916 (CO) s. 1H NMR (acetone-d6, δ) 4.02 (dd, 1H, 3JHH = 11.1 Hz,
EXPERIMENTAL SECTION
■
All reactions were performed in argon atmosphere using the Schlenk
technique. Low-temperature experiments were performed using an
ethanol−dry ice mixture as the cooling liquid. The commercially
available tetrahydrofuran, diethyl ether, benzene, and toluene were
dried over sodium benzophenone ketyl and distilled in an argon
atmosphere immediately prior to use. Saturated hydrocarbons
(pentane, hexane, and 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. The
commercially available silica gel (70−230 mesh, 60 Å, Aldrich) was
evacuated and saturated with inert gas immediately prior to use.
2JHP = 13.04 Hz, CHP(O)Ph2), 4.60 (dd, 1H, 3JHH = 11.1 Hz, 3JHP
=
15.6 Hz, CHPh), 5.53 (s, 5H, Cp), 6.9−8.1 (m, 15H, Ph). 31P{1H}
NMR (acetone-d6, δ) 31.75. Upon reaction in refluxing THF for 6 h,
Re3 was obtained in yield of 59%.
Reaction between Mn1 and HP(O)Ph2. (a) A solution of Mn1
(100 mg, 0.359 mmol) and HP(O)Ph2 (72.6 mg, 0.359 mmol) in
Et2O (5 mL) was stirred at room temperature for 24 h (after 3 h
stirring, the formation of an abundant yellow precipitate was already
observed and the solution color changed from red to orange). The
precipitate formed was separated by decantation and dried in vacuo to
yield Mn3 (135.5 mg, 78.5%) as a yellow powder. To obtain the
analytically pure substance, the powder of Mn3 was dissolved in
dichloromethane (1 mL) and chromatographed on a silica gel column
(1 cm × 10 cm) at low temperature (below −20 °C). The yellow
fraction of the product was eluted with Et2O−CH2Cl2 (1:2) and the
eluate was evaporated to dryness. The residue was washed with
pentane (3 × 5 mL) and dried in vacuo to yield 114 mg of Mn3 (66%).
Calculated for C27H22MnO3P, %: C, 67.51; H, 4.62; Mn, 11.44. Found,
%: C, 67.51; H, 4.86; Mn, 10.0. IR (THF, ν, cm−1) 1976 (CO) s, 1920
HP(O)(C6F5)2,1e HP(O)Ph2,29 and HP(S)Ph2 were prepared
30
according to the literature procedures. The commercially available
diethyl phosphite (Acros Organics) was distilled in vacuo over CaH2
prior to use.
IR spectra were recorded on a Specord M80 IR spectrophotometer
(Carl Zeiss, Germany). 1H, 31P, 19F, and 13C NMR spectra were
measured on Bruker Avance 300 (1H at 300.1 MHz and 31P at 121.5
MHz), Bruker Avance 400 (1H at 400.1 MHz, 31P at 161.98 MHz, 19
F
at 376.50 MHz, and 13C 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.
Reaction between Cp(CO)2ReCCHPh (Re1) and HP(O)-
(C6F5)2. A solution of Re1 (100 mg, 0.244 mmol) and HP(O)(C6F5)2
(93.2 mg, 0.244 mmol) in THF (5 mL) was refluxed for 4 h. The
reaction mixture was concentrated and hexane was added (∼10 mL).
The precipitate formed was separated by decantation and dried in
vacuo to yield the olefin complex Cp(CO)2Re{η2-PhCHCHP(O)-
(C6F5)2} (Re2) (145 mg, 75%) as a grayish-white crystalline powder.
Calculated for C27H12F10O3PRe × 0.5THF, %: C, 42.10; H, 1.95; F,
22.96. Found, %: C, 42.34; H, 2.31; F, 22.12. IR (THF, ν, cm−1) 1988
(CO) s, 1920 (CO) s, 1644 (CC) w. 1H NMR (acetone-d6, δ) 1.78
(q, 4H, CH2 from 0.5 THF), 3.61 (t, 4H, O−CH2 from 0.5 THF),
1
(CO) s. H NMR (acetone-d6, δ) 3.99 (br.m, 1H, CHP(O)Ph2),
4.55 (br.m, 1H, CHPh), 4.71 (s, 5H, Cp), 7.08−8.19 (m, 15H, Ph).
31P{1H} NMR (acetone-d6, δ) 30.64. (b) When the reaction between
Mn1 and HP(O)Ph2 was performed in THF for 6 h, complex Mn3
was obtained in yield of 37.5%. The same reaction in the presence of
Et3N afforded the diphosphine dioxide Ph2P(O)C(Ph)H−CH2P(O)-
Ph2 as the main product isolated in yield of 17% as a white powder
1
poorly soluble in the most of solvents. H NMR (CD2Cl2, δ) 2.75
(br.s, 1H, CH2), 3.20 (br.s, 1H, CH2), 4.28 (br.s, 1H, CHPh), 6.9−8.0
G
DOI: 10.1021/acs.organomet.6b00626
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Organometallics
Article
(m, 25H, Ph). 31P{1H} NMR (CD2Cl2, δ) 28.58 (br.s, 1P,
CH2P(O)Ph2), 33.59 (br.s, 1P, C(Ph)HP(O)Ph2).
corresponding to the π-olefin complex Cp(CO)2Re{η2-PhCH
CHP(O)(OEt)2} (Re6) (νCO, cm−1 1984 s, 1912 s) appeared. The
solution was evaporated to dryness. The residue was dissolved in
toluene (1 mL) and chromatographed on a silica gel column (1 × 10
cm) below −20 °C. The first yellow-orange fraction of Re1 was eluted
with pure toluene. The second colorless fraction of the main product
was eluted with acetone−toluene (1:5), and the eluate was evaporated
to dryness. The residue was recrystallized from toluene, and the
resulting crystals were washed with triturating in pentane (5 mL) to
afford Re6 (75.3 mg, 56%) as a white powder. Calculated for
C19H22ReO5P, %: C, 41.68; H, 4.51. Found, %: C, 41.86; H, 4.58. IR
(toluene, νCO, cm−1) 1984 s, 1912 s. 1H NMR (acetone-d6, δ) 1.19 (t,
3H, CH3, 3JHH = 6.7 Hz), 1.34 (t, 3H, CH3, 3JHH = 6.8 Hz), 3.05 (br.d,
1H, CH P(O)(OEt) 2, 2JHP ≈ 8.2 Hz), 3.98 (q, 2H, CH2, 3JHH = 6.7
Hz), 4.13 (q, 2H, CH2, 3JHH = 6.8 Hz), 4.37 (dd, 1H, CHPh, 3JHP(cis)
Reaction between Re1 and HP(S)Ph2. (a) To a solution of Re1
(100 mg, 0.244 mmol) and HP(S)Ph2 (53.3 mg, 0.244 mmol) in
benzene (5.5 mL) was added Et3N (34 μL, 0.244 mmol). The reaction
mixture was stirred at room temperature for 48 h (as far as the reaction
proceeded, the orange mixture became less colored) and evaporated to
dryness. The residue was dissolved in toluene (1 mL) and hexane (10
mL) was added slowly to afford on cooling white crystals which were
separated by decantation and dried in vacuo. The yield of
Cp(CO)2Re{η2-PhCHCHP(S)Ph2} (Re5) was 143 mg (93%).
Calculated for C27H22O2PReS, %: C, 51.66; H, 3.53; P, 4.93; Re,
29.66; S, 5.11. Found, %: C, 51.90; H, 4.01; P, 5.06; Re, 29.5; S, 4.93.
1
IR (THF, νCO, cm−1) 1984, 1912. H NMR (C6D6, δ) 3.96 (dd, 1H,
3JHH = 10.4 Hz, 2JHP = 10.8 Hz, CHP(S)Ph2), 4.85 (s, 5H, Cp), 5.12
3
3
3
= 16.6 Hz, JHH(trans) = 11.04 Hz), 5.60 (s, 5H, Cp), 6.99 (tm, 1H, p-
(dd, 1H, JHH = 10.4 Hz, JHP = 19 Hz, CHPh), 6.9−8.3 (m, 15H,
C6H5), 7.11−7.24 (m, 4H, o- and m-C6H5). 31P{1H} NMR (acetone-
Ph). 31P{1H} NMR (C6D6, δ) 56.08.
d6, δ) 33.42.
Single crystals of Re5 suitable for the X-ray diffraction study were
obtained by a slow diffusion of hexane into a solution of this complex
in CDCl3 in a NMR tube.
Reaction between Mn1 and HP(O)(OEt)2. A solution of Mn1
(200 mg, 0.719 mmol) and diethyl phosphite (102 μL, 0.791 mmol) in
Et2O (2 mL) was stirred for 44 h at room temperature (the formation
of yellow precipitate was observed and the solution color changed
from red to yellow-brown). Hexane (10 mL) was added, and the
precipitate was separated by decantation and dried in vacuo. The
residue was dissolved in toluene (1 mL) and chromatographed on a
silica gel column (10 × 1 cm) below −20 °C. The light-pink fraction
of Mn1 was eluted by pure toluene, and the second yellow fraction of
Cp(CO)2Mn{η2-PhCHCHP(O)(OEt)2} (Mn6) was eluted with
acetone−toluene (1:5). The eluate was evaporated to dryness, the oily
residue solidified when left to stand, and the resulting yellow solid
washed with triturating in pentane (5 mL) to yield Mn6 (153.3 mg,
51.2%) as a yellow powder. Calculated for C19H22MnO5P, %: C, 54.82;
H, 5.33; Mn, 13.20. Found, %: C, 54.74; H, 5.31; Mn, 13.20. IR (Et2O,
(b) Upon reaction between Re1 (50 mg, 0.122 mmol) and
HP(S)Ph2 (25.3 mg, 0.134 mmol) in refluxing THF (5 mL) in the
presence of Et3N (17 μL, 0.122 mmol), complex Re5 was obtained in
yield of 89% (67.8 mg) as a white powder. IR (THF, νCO, cm−1) 1984
1
s, 1912 s. H NMR (acetone-d6, δ) 4.61 (m, 2H, C(P)HCHPh),
5.32 (s, 5H, Cp), 7.0−8.3 (m, 15H, Ph). 31P{1H} NMR (acetone-d6,
δ) 54.55.
Reaction between Mn1 and LiSPPh2. To a solution of
diphenylphosphine sulfide (67.4 mg, 0.309 mmol) in THF (2 mL),
a 1 M solution of LiOt-Bu in THF (325 μL, 0.325 mmol) was added
using a microsyringe, and the mixture was stirred for 10 min. The
resulting solution of LiSPPh2 was added through a cannula to a
solution of Mn1 (86 mg, 0.309 mmol) in THF (2 mL), an instant
change in the solution color from red to brown-red being observed.
The mixture was stirred for 10 min and cooled to −60 °C and HBF4·
OEt2 (44 μL, 0.325 mmol) was added. After warming to room
temperature, the IR spectrum of the reaction mixture displays only the
bands corresponding to the π-olefin complex Cp(CO)2Mn{η2-
PhCHCHP(S)Ph2} (Mn5) (νCO, cm−1 1980 s, 1920 s) appeared.
The solution was evaporated to dryness. The residue was dissolved in
toluene (1 mL) and chromatographed on a silica gel column (1 × 10
cm) below −20 °C. The first red-violet fraction of the binuclear μ-
vinylidene complex [Cp(CO)2Mn]2CCHPh was eluted with pure
toluene. The second yellow fraction of Mn5 was eluted with THF−
toluene (1:5), and the eluate was concentrated under reduced pressure
until the total volume of about 5 mL. At the end of concentration, the
solution color became green, and a yellow precipitate formed. The IR
spectrum of the mother liquor displays additional low-intensity bands
at νCO 1930, 1848, cm−1. On keeping in a freezer, the mother liquor
became brown. The precipitate was separated from the mother liquor
by decantation, washed with hexane (2 × 2 mL), and dried in vacuo to
1
νCO, cm−1) 1984 s, 1928 s. IR (THF, νCO, cm−1) 1980 s, 1924 s. H
NMR (acetone-d6, δ) 1.19 (t, 3H, CH3), 1.40 (t, 3H, CH3), 2.81 (dd,
1H, CH P(O)(OEt) ), 3.96 (m, 2H, CH2), 4.20 (dq, 2H, CH2),
2
4.52 (dd, 1H, CHPh), 4.86 (s, 5H, Cp), 7.07 (t, 1H, p-C6H5), 7.21−
7.28 (m, 4H, o- and m-C6H5). 31P{1H} NMR (acetone-d6, δ) 33.13.
1
31P{1H} NMR (C6D6, δ) 33.13. 13C{ H} NMR (C6D6, 150.93 MHz,
3
3
δ) 16.28 (d, 2C, JCP1 = 5.4 Hz, CH3), 16.45 (d, 2C, JCP = 6.0 Hz,
2
CH3), 37.59 (d, 1C, JCP = 183.4 Hz, CHP(O)), 58.66 (d, 1C, JCP
= 4.7 Hz, CHPh), 61.17 (d, 2C, 2JCP = 6.7 Hz, CH2), 61.34 (d, 2C,
2JCP = 5.4 Hz, CH2), 86.03 (s, 5C, Cp), 125.94 (br. s, 2C, o-C6H5),
126.27 (s, 1C, p-C6H5), 128.66 (s, 1C, m-C6H5), 144.74 (d, 1C, 3JCP
10.7 Hz, ipso-C6H5), 229.65 and 234.82 (s, 1C each, CO).
=
Reaction between Mn1 and LiOP(OEt)2. To a solution of
diethyl phosphite (46.3 μL, 0.359 mmol) in THF (2 mL), a 1 M
solution of LiOt-Bu in THF (359 μL, 0.359 mmol) was added using a
microsyringe and stirred for 10 min. The resulting solution of
LiOP(OEt)2 was added through a cannula to a solution of Mn1 (100
mg, 0.359 mmol) in THF (2 mL) (the solution darkened). The IR
spectrum displayed the absorption bands of the anionic complex
Li+[Cp(CO)2Mn−C(P(O)(OEt)2)CHPh]− (Mn7) (νCO, cm−1
1884 s, 1816 m, 1776 s). The solution was stirred for 20 min, multiple
excesses of a saturated aqueous solution of NH4Cl added, and the
mixture stirred overnight. As far as protonation proceeded, the IR
bands of protonation product (Mn6) (νCO, cm−1 1980 s, 1924 s)
increased in intensity. The resulting dark-green solution was
evaporated to dryness. The residue was dissolved in toluene (2 mL)
and chromatographed on a silica gel column (1 cm × 10 cm) below
−20 °C. The first blue-green band of unknown product was eluted
with pure toluene, the second yellow-brown fraction eluted with
acetone−toluene (1:10), and the yellow fraction of pure Mn6 eluted
with acetone−toluene (1:5). The yellow eluate was evaporated, and
the resulting oily residue crystallizes when left to stand. The obtained
yellow crystals were washed with hexane upon triturating with spatula
and dried in vacuo to yield 98.2 mg of Mn6 (66%). The spectral data
of the product correspond to those given above.
yield a yellow powder of Mn5 (72.7 mg, 47%). IR (toluene, νCO
,
1
cm−1) 1980 s, 1924 s. H NMR (CD2Cl2, δ) 3.86 (br.m, 1H, 
CHP(O)Ph2), 4.24 (s, 5H, Cp), 4.44 (br.m, 1H, CHPh), 7.03 (br.t,
1H, p-C6H5 from P(S)Ph), 7.10−7.3 (3 br.m, 6H, o- and m-C6H5),
7.41 (br.t, 2H, m-C6H5 from P(S)Ph), 7.53 (br.t, 4H, o-C6H5 from
P(S)Ph), 8.1 (br.m, 2H, o-C6H5 from CHPh). 31P{1H} NMR
(CD2Cl2, δ) 54.08.
Reaction between Re1 and LiOP(OEt)2. To a solution of diethyl
phosphite (35 μL, 0.268 mmol) in THF (2 mL), a 1 M solution of
LiOt-Bu in THF (268 μL, 0.268 mmol) was added using a
microsyringe, and the mixture was stirred for 10 min. The resulting
solution of LiOP(OEt)2 was added through a cannula to a solution of
Re1 (100 mg, 0.244 mmol) in THF (2 mL), an instant change in the
solution color from orange to light-brown being observed. The IR
spectrum displayed bands of an anionic complex Li+[Cp(CO)2Re−
C(P(O)(OEt)2)CHPh]− (νCO, cm−1 1876 s, 1804 w, and 1764 s).
The mixture was stirred for 10 min and cooled to −60 °C, and HBF4·
OEt2 (40 μL, 0.293 mmol) was added. In the IR spectrum, the
absorption bands of the anionic complex disappeared, and new bands
Reaction between Cp(CO)2Mn{η2-HCCPh} (Mn9) and HP-
(O)(C6F5)2 in Et2O. A solution of cymantrene (102 mg, 0.5 mmol)
H
DOI: 10.1021/acs.organomet.6b00626
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
and phenylacetylene (66 μL, 0.6 mmol) in Et2O (20 mL) was
irradiated externally by a DRL-400 UV lamp (400 W) with vigorous
stirring for 1 h maintaining the temperature below −60 °C by dry ice−
ethanol bath. The solution gained a crimson color corresponding to
Cp(CO)2Mn(Et2O). Upon slow warming, the mixture became brown,
and the IR spectrum displayed bands of Cp(CO)2Mn(η2-PhCCH)
(Mn9) (νCO, cm−1 1976 s, 1912 s). HP(O)(C6F5)2 (152.8 mg, 0.4
mmol) was added to the resulting solution of Mn9, and the mixture
was stirred for 5 days at room temperature. After stirring overnight, a
few yellow crystals appeared on the flask walls, which was followed by
abundant precipitation of a flocculent white solid over the next days.
The precipitate was separated by decantation, washed with diethyl
ether, and dried in vacuo to afford 71.1 mg of (C6F5)2P(O)−
CH2CHPh−P(O)(C6F5)2 (41% based on HP(O)(C6F5)2) as a white
powder. Calculated C32H8F20O2P2, %: C, 44.37; H, 0.93. Found, %: C,
AUTHOR INFORMATION
Corresponding Author
*E-mail: ustynyuk@ineos.ac.ru. Tel.: + 7 (495) 135 50 64; +7
(916) 228 33 69.
■
ORCID
Nikolai A. Ustynyuk: 0000-0002-3859-4145
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was financially supported by the Russian Foundation
for Basic Research (Project No. 15-03-04745). We are grareful
to Prof. A. S. Peregudov for 13C NMR and 2D NMR spectral
studies.
1
44.20; H, 1.05. H NMR (CD2Cl2, δ) 3.41 (br.s, 1H, CHH), 3.60
(br.s, 1H, CHH), 4.75 (br.s, 1H, CHPh), 7.08 (br.s, 3H, m and p-
C6H5), 7.40 (br.s, 2H, o-C6H5). 31P{1H} NMR (CD2Cl2, δ) 15.27 (d,
3
3
1P, JPP = 67 Hz), 22.31 (d, 1P, JPP = 67 Hz). 19F{1H} NMR
(CD2Cl2, δ) −159.99, −159.39, 158.83, −158.07 (t, 8F, m-C6F5),
−145.67, −144.41, −144.35, −143.88 (t, 4F, p-C6F5), −132.68,
REFERENCES
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ASSOCIATED CONTENT
■
S
* Supporting Information
(7) Complexes with coordinated PO forms such as (PO)M are
known mainly for rare-earth metals,7a early transition metals,7b,c and
group 13 elements.7d−f (a) Kapoor, P. N.; Saraswati, R.; McMahon, I.
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The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.6b00626.
Selected bond lengths, angles, crystal data, data
collection, and structure refinement parameters for
complexes Re2 and Re5; 2D NMR spectrum for Mn6;
calculation data for the reaction between Mn1 and
HP(O)(OMe)2 (PDF)
Crystallographic data for Re2 and Re5 (CIF)
Computed Cartesian coordinates and energies for Mn1 +
HP(O)Me2 in the gas phase and Et2O and Mn1 +
HP(O)(OMe)2 in the gas phase (XYZ)
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nickel,8b−d and rhodim8e,f hydrophosphoryl complexes of the (PO)M
type are known: (a) Graux, L. V.; Giorgi, M.; Buono, G.; Clavier, H.
Organometallics 2015, 34, 1864−1871. (b) Pascu, S. I.; Coleman, K. S.;
I
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2
the uncoordinated terminal alkyne Tolp C[Ph2P(O)]−CCH:
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,
cm−1) 1900 s, 1822 s. 1H NMR (CD2Cl2, δ) 1.60 (d, 9H, CH3, 2JHP
=
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3
3JHα,Hβ = 18.3 Hz, JHα,P = 43.3 Hz), 11.39 (1H, X part of the AX
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1
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3
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P(O)(Oi-Pr)2 rather than the trans isomer was produced in this
reaction..
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1
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K
DOI: 10.1021/acs.organomet.6b00626
Organometallics XXXX, XXX, XXX−XXX