A Commercially Available Ruthenium Compound for Catalytic Hydrophosphination

Article abstract of DOI:10.1002/ijch.201900070

Hydrophosphination with a commercially available ruthenium compound, bis(cyclopentadienylruthenium dicarbonyl) dimer ([CpRu(CO)₂]₂), was explored. Styrene derivatives or Michael acceptors react readily with either primary or secondar

Full text of DOI:10.1002/ijch.201900070

Full Paper
DOI: 10.1002/ijch.201900070
A Commercially Available Ruthenium Compound for
Catalytic Hydrophosphination
Michael P. Cibuzar,[a] Steven G. Dannenberg,[a] and Rory Waterman*[a]
Synthetic chemists continue to be inspired by the exploits of Profs. Stephen Buchwald and John Hartwig. We are delighted to
share these results in celebration of their well-deserved Wolf Prize.
Abstract: Hydrophosphination with a commercially available pensive and commercially available UV/A 9 W lamp. In
ruthenium
compound,
bis(cyclopentadienylruthenium comparison to related photoactivated hydrophosphination
dicarbonyl) dimer ([CpRu(CO)2]2), was explored. Styrene reactions with [CpFe(CO)2]2 as a catalyst, these ruthenium-
derivatives or Michael acceptors react readily with either catalyzed reactions proceed at greater relative rates with
primary or secondary phosphines in the presence of lower catalyst loadings.
0.1 mol% of [CpRu(CO)2]2 under photolysis with an inex-
Introduction
liberation from the metal through a fully developed stoichio-
metric cycle akin to a catalytic process.
Selective PÀ C bond formation continues to be a synthetic
challenge despite the myriad of applications phosphines have
in synthetic and catalytic chemistry.[1] Metal-catalyzed hydro-
phosphination is at the fore of PÀ C bond formation because it
proceeds with 100% atom economy with the potential for high
selectivity, producing regio-, chemo-, and enantiospecific
products (Eq 1).[2] The transformation appears to be on the rise
in global interest and mechanistic understanding continues to
increase.[1h]
Substantial advances in iron-catalyzed hydrophosphination
have been made in recent years. The field has been led by the
groups of Gaumont using iron salts for the selective hydro-
phosphination of alkenyl arenes, Nakazawa for iron promoted
hydrophosphination of internal alkenes with diphenyl
phosphine, and Webster for iron catalyzed hydrophosphination
of alkenes and alkynes with both primary and secondary
phosphines.[4e,7] We have reported photoactivated hydrophos-
phination catalysis with [CpFe(CO)2]2 (1), including rapid
double hydrophosphination of terminal alkynes to form 1,2-
diphosphinoethane products.[3e,i] This study targeted the poten-
tial hydrophosphination reactivity of [CpRu(CO)2]2 (2) under
photoactivation with a key question: Would the reactivity and
activity of ruthenium be substantially different than iron? This
question informs a broader hypothesis that limitations in iron-
catalyzed hydrophosphination can be overcome with greater
understanding, even of its congener. Addressing this hypoth-
esis would both advance hydrophosphination in general as
well as aid in expanding this reaction in a more sustainable
way.
ð1Þ
However,
hydrophosphination
catalysis
has
its
challenges.[2b] Precious metal catalyzed reactions remain
among the most popular and lead the field in selectivity.[2a,b,3]
Many d0 metal catalysts exhibit great activity and substrate
scope but still have substantial limits. Recent noteworthy
successes including high enantioselectivity and the synthesis
of other value-added molecules such as chelating ligands and
phosphorus heterocycles demonstrate that continued study of
this transformation will be highly fruitful.[3j,4]
More than merely a comparison of congeners, the
similarity of activation via photo-induced splitting of the
dimers into 17-electron intermediates is critical to this
comparison. Whereas 1 is activated into two equivalents of the
Exploration of ruthenium-based hydrophosphination reac-
tivity has been productive and intriguing. In a report by
Dixneuf, simple ruthenium complexes, including Cp*Ru
(COD)Cl and Cp*Ru(PPh3)2Cl, were used to generate vinyl
phosphines from propargyl alcohols. However, reaction con-
*
17-electron compound Cp(CO)2Fe by visible light, the
ruthenium compound 2 is activated by near UV light (~
*
330 nm) to also yield two Cp(CO)2Ru (Eq 2).[8] The related
°
ditions were somewhat harsh at >100 C for 24 hours, with
catalytic base, and relatively high catalyst loadings.[5] Rosen-
berg and coworkers have garnered tremendous mechanistic
understanding through investigation of stoichiometric PÀ C
bond formation with ruthenium.[1h,6] At the core of that work is
a concerted, inner-sphere PÀ C bond forming event, most likely
an insertion reaction, as well as an understanding of product
[a] M. P. Cibuzar, S. G. Dannenberg, R. Waterman
Department of Chemistry, University of Vermont, Burlington,
Vermont 05405-0125, United States;
E-mail: rory.waterman@uvm.edu
Supporting information for this article is available on the WWW
under https://doi.org/10.1002/ijch.201900070
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Table 1. Hydrophosphination of styrene substrates and Michael acceptors.
Substrate
Time[a]
60
Major product
Minor product
Conversion[b]
100
(95:5)
100
(95:5)
40
100
(95:5)
60
70
100
(95:5)
100
(99.6:0.4)
60
95
(96:4)
120
100
(93:7)
12
100[c][d]
(81:19)
18 h
1
Products where unambiguously identified by comparing H and 31P spectra to literature values. Products where not isolated and conversions
were determined by integration of 31P NMR spectra and confirmed by integration of 1H NMR when peaks where not obscured by overlapping
with starting material or other products. If there is not significant noise in the baseline, 31P NMR is generally accurate for integration of
1
1
products, though not as accurate as H NMR. As a result, some ratios may be slightly less accurate than if H NMR integration could be
employed. Consumption of unsaturated substrate was determined by 1H NMR spectroscopy. [a] Time in minutes unless specified. [b] values in
parenthesis are ratio of major to minor products. [c] catalyst loading=1 mol%. [d] Reaction run at a ratio of 1:1 alkene to phosphine.
photoactivation is a key piece of the comparative study of
these compounds.
optimal because lower phosphine loadings increased formation
of tertiary phosphine products via double PÀ H activation,
while higher loadings did not provide improved selectivity.
Some initial screening reactions were conducted at 1.0 mol%
catalyst loading, but it was found that 0.1 mol% of 2 achieved
high conversions for all substrates tested in two hours or less
of reaction time. Thus, activity was not adversely affected by
the decreased catalyst loading. Reactions were irradiated using
a commercial UV/A lamp (λ=360 nm) and shielded from
ambient light. The UV/A lamp does produce excess heat and
ð2Þ
Results and Discussion
Hydrophosphination of activated alkenes with phenylphos-
phine was initially explored. Treatment of a three-to-one
mixture of phenylphosphine and alkene with 0.1 mol% of 2 in
benzene-d6 at ambient temperature under irradiation by a broad
wavelength 9-W UV/A lamp (See SI for spectrum) resulted in
hydrophosphination of the alkene in conversions greater than
90% as determined by 1H and 31P NMR spectroscopy
(Table 1). Three equivalents of phosphine were generally
°
shielded reactions were measured at temperatures of 25–30 C,
depending on the total reaction time and if the photoreaction
chamber had recently been in use or completely cooled.
Precise measures to control reaction temperatures within the
°
range of 25–30 C were not undertaken.
Increased, and different, activity was observed with 2 as
compared to 1. A difference in reactivity was observed for
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Table 2. Hydrophosphination of various substrates with 2.
Substrate
Time/h
Major product
Minor product
Conversion
100
(91:9)
12
(93:7)
100[a][b]
(97:3)
13[f]
2
Products unknown
Products unknown
Products unknown
Product unknown
18
23
72
(97:3)
72
26
None
None
None
0[f]
4[a][e]
46[c][e]
(45:1)
48
Products unknown
None
24
2
None
0 [d]
24[e]
(21:3)
Products unknown
All reactions run with 1 mol% of 2, unless specified, and under irradiation in the near UV. Product conversions determined by integration of 31
P
NMR spectra. Consumption of unsaturated substrate determined by integration of 1H NMR spectra. [a] 1 equiv. unsaturated substrate: 1 equiv.
phosphine. [b] Diphenylphosphine used instead of phenylphosphine. [c] 4 equiv. unsaturated substrate: 1 equiv. phosphine. [d] 1 equiv.
unsaturated substrate: 2 equiv. phosphine. [e] Consumption of phosphine, determined by 31P NMR spectroscopy. [f] 0.1 mol% 2.
electron rich and poor styrene substrates with 1, with electron-
poor styrene substrates being more readily converted.[3e] This
trend was not observed with 2. For some substrates, the
opposite trend was observed with more electron-rich styrene
substrates reacting with a greater relative rate. Steric bulk also
appears to increase reactivity. However, a clear and conclusive
pattern is difficult to discern due to the fast and similar
reaction times of styrene and styrene derivatives. First, and
unlike 1, styrene was a viable substrate, with complete
consumption in 60 minutes. Electron donating para-alkyl
substituted styrene derivatives, tBu and Me, were both
completely consumed in less than one hour under irradiation at
ambient temperature. Complete consumption of the bulkier p-
tert-butylstyrene occurred faster than p-methylstyrene. Elec-
tron-poor styrene derivatives required similar, in the case of
the bulkier p-trifluoromethylstyrene, or longer reaction times
in the case of p-bromostyrene to be fully consumed with each
undergoing reaction times of 60 and 70 minutes, respectively,
for completion.
Michael acceptors were excellent substrates for this
reaction, as anticipated. When using methyl acrylate as the
unsaturated substrate, complete consumption of methyl
acrylate was observed in less than 12 minutes, and produced
the secondary and tertiary hydrophosphination products in
93% and 7% yields, respectively.[2b,3g,7b, 9] In control reactions
run under irradiation in the absence of 2, complete consump-
tion of acrylate substrate was observed after 4 hours (95:5).
The UV initiated hydrophosphination of Michael acceptors is
well established.[10]
1 mol% of 2 under irradiation afforded the 1,4-addition
product in 91% conversion at 2 hours reaction time as
determined by NMR spectroscopy (Table 2). In contrast, the
reaction of cyclohexylphosphine (3 eq) and 2,3-dimethyl,1-3-
butadiene with 1 mol% of 2 under irradiation allowed for
observation of the 1,4-addition product in 9% conversion at
2 hours and 12% at 18 hours of reaction time. Steric factors
may be at work, but the substantial difference in activity
indicates that electronic factors cannot be ignored.
The reversed behavior of electron donating and with-
drawing substituents is not the most important distinction
between the iron and ruthenium compounds as hydrophosphi-
nation catalysts. Treatment of a 1:1 mixture of diphenylphos-
phine and styrene with 1 mol% of 2 for nearly one day under
irradiation resulted in the 97% conversion to the expected
hydrophosphination as determined by 31P NMR. Reducing the
catalyst loading to 0.1 mol% of 2 resulted in 84% conversion
to the hydrophosphination product after 24 hours and a 92%
conversion after 48 hours. While iron compound 1 had a
particularly low conversion with styrene (NB: there appeared
to be some competitive radical chemistry for this substrate),
para-substituted derivatives were effective substrates.[3e] How-
ever, even for the most active styrene derivatives, iron exhibits
more modest activity than ruthenium does. Thus, it is
reasonable to conclude that 2 is a more active catalyst for
hydrophosphination catalysis than is 1. This increase in
activity is offset by the substantial difference in cost for these
two catalysts. A recent search of the Sigma-Aldrich web
catalog revealed pricing for 1 of approximately 0.38 USD per
gram and 361 USD per gram for 2. From an economic
standpoint, it seems more likely that the activity of iron can be
The identity of the phosphine is important. Reaction of
phenylphosphine (3 eq) and 2,3-dimethyl,1-3-butadiene with
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increased to match that of ruthenium rather than the loading
reduced to justify its cost. That coarse analysis supports a
sustainability argument for the continued study of iron
catalysts for this reaction.
throughout the course of the reaction and that this reactivity is
photocatalysis rather than photoactivation as seen for the
related iron compound, 1. We have seen photocatalytic hydro-
phosphination that results from activation of a ZrÀ P bond.[3j,14]
The mechanism of hydrophosphination is still under
consideration, but the literature guides our thinking to an
acceptable working mechanistic hypothesis. The first issue to
consider is PÀ H bond activation. Irradiation with 360 nm light
The comparative study for 1 and 2 is limited to
diphenylphosphine because compound 1 is so poorly effective
in hydrophosphination with primary phosphine substrates.
Indeed, our main objective in investigating ruthenium was the
potential for observing α-phosphinidene elimination with a
heavier metal that may promote singlet-like phosphinidene
chemistry rather than the triplet-like phopshinidene transfer
promoted by 1.[11] The absence of phosphinidene transfer with
2 and the observation of hydrophosphination instead is
consistent with our developing hypothesis that greater
reactivity with unsaturated substrates diminishes transfer of
low-valent fragments.[12] In any case, comparison of the same
phosphine and unsaturated substrates for both catalysts is
important for benchmarking hydrophosphination catalysis.[9b]
Other substrates, however, were not amenable to hydro-
phosphination using 2. Reaction of 1-hexene with phenyl-
phosphine and 1 mol% of 2 under irradiation resulted in only
4% consumption of 1-hexene to the secondary phosphine
product. Similar results were obtained in reactions with ethyl
vinyl ether and cyclohexene (Table 2). Unactivated alkenes are
challenging substrates for any heterofunctionalization reac-
tions, and only one catalyst is effective in the hydrophosphina-
tion of these substrates.[3j][9b] Alkynes are more amenable than
unactivated alkenes, but these are still poor substrates by any
reasonable measure. Reaction of phenylacetylene and phenyl-
phosphine with 1 mol% of 2 under irradiation resulted in 46%
consumption of phosphine by 31P NMR spectroscopy (Ta-
ble 2). However, the products were largely unidentified and
primarily not the expected vinylphosphine product or possible
1,2-bis(phenylphosphino)-1-phenylethane, which is the antici-
pated product of iron catalyst 1 or Cp(CO)2FeMe by
Nakazawa in a double hydrophosphination reaction.[3i,13] Only
trace quantities of the hydrophosphination product were
observed. Identification of the other products was unsuccess-
ful. Compared with terminal alkynes, internal alkynes were
relatively more successful substrates for hydrophosphination
with 2. Treatment of diphenylacetylene and phenylphosphine
(3 eq) with 1 mol% of 2 under irradiation for 2 hours afforded
24% conversion to the vinyl product as a 7:1 ratio of Z:E
isomers (Table 2). Extended reaction times appear to lead to
Z:E isomerization as a 4:1 ratio is observed after 18 hours
with little increase in overall yield. Vinyl phosphine isomer-
ization is consistent with the literature.[14] The reaction appears
to ultimately be halted by decomposition of the catalyst.
Unfortunately, the trimethylsilylacetylene was unreactive in
the conditions screened.
*
produces two equivalents of Cp(CO)2Ru , which can coopera-
tively cleave the PÀ H bond of a phosphine substrate,
generating Cp(CO)2RuPRR’ and Cp(CO)2RuH, akin to com-
pound 1.[3e] In the case of iron catalysis, the Cp(CO)2FeH
intermediate is unstable and reforms 1, but Cp(CO)2RuH is
more thermally robust and hydridic.[15] Thus, it is reasonable to
suspect that Cp(CO)2RuH could also react with phosphine to
also form Cp(CO)2RuPRR’ derivatives, which are known.[16]
To test the first proposal, a stoichiometric reaction of 2 with
diphenylphosphine, both Cp(CO)2RuPPh2 and Cp(CO)2RuH
1
are observed by H and 31P NMR spectroscopy (benezene-d6,
Eq 3).[17] To test the latter supposition, 2 was treated with two
equivalents of diphenylphosphine and monitored by NMR
spectroscopy over the course of 24 hours. In that reaction, the
relative concentration of Cp(CO)2RuH rises and then falls with
an increase in Cp(CO)2RuPPh2. This observation is consistent
a productive reaction of the ruthenium hydride and phosphine.
However, this is a tenuous conclusion because both reaction
mixtures decompose to complex mixtures over the course of
24 hours. We are confident, however, that unlike the iron
system 2 is merely a precatalyst.
ð3Þ
Next, it is important to consider PÀ C bond formation.
Direct study in this system is problematic with the two process
that lead to a phosphido intermediate (vide supra). The
literature provides some useful indications of a likely
mechanism. Rosenberg and coworkers provide excellent
evidence in support for a concerted, inner-sphere (e.g.,
insertion) reaction of alkenes at the RuÀ P bond of related
indenyl ruthenium phosphido compounds.[1h,6a–c] That prece-
dent provides a strong basis for a mechanistic hypothesis that
involves insertion into a RuÀ P bond in this system. There are
limitations to that supposition, though. Rosenberg’s systems,
commonly (indenyl)(PPh3)Ru=PRR’, possess significantly
different ligands, with respect to electronic effects, than the Cp
and CO ligands of 2. Moreover, Rosenberg’s compounds are
coordinately unsaturated and exhibit substantial phosphorus-
to-metal π bonding.[1h,6a–c] The relationship between these
compounds is significant nevertheless, and an insertion-based
mechanism is the working hypothesis here. It is well under-
stood that many late-metal phosphido compounds react as
nucleophiles, but the observed reactivity with styrene deriva-
tives does not support this possibility.[18] Finally, Rosenberg
Photoactivation versus photocatalysis was tested with an
initiation experiment. Styrene and three equivalents of phenyl-
phosphine were treated with 0.1 mol% of 2. The reaction
mixture was irradiated for five minutes and then kept in the
dark for the subsequent 18 hours. At that time, only 12% of
phosphine was consumed, indicating that light is required
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has demonstrated proton transfer as a product-liberating step
in a stoichiometric analogy to catalytic hydrophosphination.[1h]
That system requires a base co-catalyst to accomplish this
step, but the difference in ligands between that at 2 may allow
for proton transfer from these phosphine substrates, despite
their modest acidity.[19] Overall, our understanding of this
system is limited, and for that reason, a proposed catalytic
cycle would be too speculative to include.
Diphenylphosphine and cyclohexylphosphine are set to
À 40.0 ppm and À 111.8, respectively, in 31P NMR spectra.[22,23]
Spectral data for hydrophosphination products are consistent
with literature reports.[3i,j,9b,14,21–24]
Procedure for Catalytic Experiments
For reactions with 1 mol% of 2: In an N2 filled dry box,
1.35 mmol of phosphine (or 0.45 mmol where applicable) and
0.45 mmol of unsaturated substrate were measured and mixed
in ca. 0.5 mL benzene-d6. This solution was then pipetted into
a scintillation vial containing 2 mg (0.0045 mmol) 2 and
quickly transferred into an NMR tube wrapped with aluminum
foil.
Concluding Remarks
UV irradiation of the commercially available compound 2
promotes efficient hydrophosphination with low catalyst
loading under low intensity UV light at ambient temperature.
Greater activity and expanded substrate scope were observed
compared to the iron derivative, 1. 2 is significantly more
active for hydrophosphination of alkenes with primary
phosphines then previously reported iron and ruthenium
compounds. Universal comparison to other reported catalysts
for other substrates is difficult due to differences in substrate
scope, selectivity, conditions, price, and loading. This high-
lights the need for benchmarking in catalysis.[20] In particular,
2 is successful with hydrophosphination of primary phosphine
substrates that have eluded 1. In comparing diphenylphos-
phine, both compounds readily utilize styrene derivatives and
Michael acceptors were readily reacted, but 2 is substantially
more reactive. Alkynes and unactived alkenes gave poor
reactivity but support indications of an insertion-based hydro-
phosphination mechanism, predicted based on literature re-
ports. More extensively studied indenyl-ruthenium compounds
can do stoichiometric hydrophosphination but do not exhibit
catalytic turnover.[1h] These differences suggest that additional
design and study can afford significant enhancements in iron-
catalyzed hydrophosphination through tuning of 1 and other
iron derivatives. That work is currently underway.
For reactions with 0.1 mol% 2 this procedure was slightly
modified: The phosphine and unsaturated substrates were
dissolved in ca. 0.4 mL benzene-d6, transferred to a foil-
wrapped NMR tube, and then 0.1 mL of a 0.0045 M stock
solution was syringed into the NMR tube. For both catalytic
loadings, the reactions were kept in an aluminum foil wrap
1
until initial H and 31P NMR spectra were acquired. After the
initial NMR spectra, reactions were then placed in a Rexim
G23 UV/A (9 W) lamp at room temperature and shielded from
ambient light. Periodic NMR spectra were collected until
reactivity ceased. All reactions were performed with 0.1 mol%
of 2 and 3:1 phosphine : unsaturated substrate, unless
otherwise stated.
Acknowledgements
This work was funded by the U.S. National Science
Foundation through CHE-1565658.
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Manuscript received: June 21, 2019
Revised manuscript received: August 5, 2019
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M. P. Cibuzar, S. G. Dannenberg, R.
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