Zirconium-catalyzed hydroarsination with primary arsines

Article abstract of DOI:10.1016/j.poly.2018.09.007

The zirconium compound, [κ⁵-N,N,N,N,C-(Me₃SiNCH₂CH₂)₂NCH₂CH₂NSiMe₂CH₂]Zr (1), catalyzes the hydroarsination of alkenes with primary arsines, previously unkn

Full text of DOI:10.1016/j.poly.2018.09.007

Accepted Manuscript
Zirconium-Catalyzed Hydroarsination with Primary Arsines
Christine A. Bange, Rory Waterman
PII:
S0277-5387(18)30556-4
https://doi.org/10.1016/j.poly.2018.09.007
POLY 13404
DOI:
Reference:
To appear in:
Polyhedron
Received Date:
Revised Date:
Accepted Date:
2 August 2018
4 September 2018
4 September 2018
Please cite this article as: C.A. Bange, R. Waterman, Zirconium-Catalyzed Hydroarsination with Primary Arsines,
Polyhedron (2018), doi: https://doi.org/10.1016/j.poly.2018.09.007
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Zirconium-Catalyzed Hydroarsination with Primary Arsines
Christine A. Bange and Rory Waterman*
Department of Chemistry, Discovery Hall, University of Vermont, Burlington, VT 05401, USA
rory.waterman@uvm.edu
Keywords: Hydroarsination, zirconium, arsenic, catalysis, photocatalysis
Abstract
5
The zirconium compound, [ -N,N,N,N,C-(Me
3
SiNCH
2
CH
2
)
2
NCH
2
CH
2
NSiMe
2
CH ]Zr (1),
2
catalyzes the hydroarsination of alkenes with primary arsines, previously unknown substrates for
this transformation. Irradiation in the ultraviolet, near-UV, or visible with commercially-available
light sources are critical for this catalysis. Styrene substrates are unreactive without irradiation, but
Michael acceptors give products in the dark or under irradiation with any source. These
observations suggest that the zirconium arsenido intermediate engages in insertion based
hydroarsination under photolysis, but the arsenido ligand is nucleophilic without photoexcitation.
Keywords: Hydroarsenation catalysis, zirconium, arsenide, photocatalysis, arsine
1
. Introduction
Catalytic heterofunctionalization involving group 15 elements is a proven methodology to
generate new C–E bonds for both nitrogen and phosphorus, yet catalytic hydroarsination is rare,
with only a handful of reported examples of this reaction.[1-10] Nevertheless, such a strategy
offers an atom-economical and direct route to organoarsines, but the transformation is limited to
only a handful of substrates and often precious-metal catalysts.[2-4, 9] All reported
transformations utilize secondary arsine substrates with the exception of one case that utilizes an
arsenylborane.[6] Thus far, hydroarsination with primary arsines to selectively make secondary
1

arsines remains unreported, but such products are attractive, being available for further
functionalization by conventional means.
Organoarsines have found applications in diverse fields including chemistry,[1-3, 11, 12]
materials science,[13] agriculture,[14] and as anti-cancer agents.[15, 16] Catalytic chemistry that
forms bonds to arsenic chemistry is less developed than that for lighter group pnictogens,[11] but
a notable achievement is arsenic-based ligands. Some triarylarsine ligands have outperformed
phosphorus analogues in cross-coupling[15, 17, 18] and arsination reactions.[19]
5
Our previous work on catalytic hydroarsination using [ -N,N,N,N,C-
(Me
3
SiNCH
2
CH
2
)
2
NCH
2
CH
2
NSiMe
2
CH ]Zr (1) has targeted terminal alkynes and secondary
2
arsines to provide tertiary vinyl arsine products (eqn 1).[7] Critical to that work was establishing
facile As–H bond activation at 1, which was primarily exploited for arsine dehydrocoupling but
lay the groundwork for additional As–C bond-forming catalysis. However, like the related
hydrophosphination catalysis, reactivity with diphenylarsine was ultimately limited and relative
rates of catalytic reactions were low.
(1)
Development of hydroarsination involving primary arsines would be of value. This
methodology could selectively generate either secondary or tertiary arsines from simple
precursors. Our previous work in catalytic hydrophosphination of primary phosphines with 1
2

demonstrated the selective formation of tertiary phosphine products (eqn 2, double activation).[20]
Upon slight modification of the reaction conditions, exclusively secondary phosphine products
could be achieved (eqn 2, single activation).
(2)
For 1, hydrophosphination catalysis with primary phosphines has been more facile than
reactions with secondary phosphines,[20] an idea that may be extended to arsenic. More recent
reports showed yet greater catalytic activity and a broadened substrate scope with 1 in the under
ultraviolet or visible irradiation.[21] The improved hydrophosphination activity prompted
reinvestigation into catalytic hydroarsination using 1 with primary arsines under photocatalytic
conditions. The result was the first example of a catalytic hydroarsination utilizing primary arsines
and a rare example of a photocatalytic heterofunctionalization reaction for heavier group 15
elements.
2
2
. Materials and Methods
.1 General methods
All manipulations were performed under a positive nitrogen pressure with standard Schlenk
techniques or in a glovebox using dry, oxygen-free solvents. NMR spectra were recorded on a
Bruker AXR 500 MHz spectrometer using benzene-d6 that was distilled under reduced pressure from
NaK alloy. NMR spectra are reported with reference to residual solvent signals (C
6
6
D , δ 7.16 and
1
28.0). ESI-mass spectra were collected on an Applied Biosystems 4000QTrap Pro. IR data were
3

collected on a Bruker Alpha FTIR spectrometer in hexanes. Absorption spectra were recorded
with a QuantaMaster 4 fluorescence spectrophotometer (PTI, Edison, NJ, USA) as hexanes
5
solutions. The zirconium compound [ -N,N,N,N,C-(Me
3
SiNCH
2
CH
2
)
2
NCH
2
CH
2
NSiMe
2
CH ]Zr
2
(1) was prepared according to the literature method.[22] All other chemicals were obtained from
commercial suppliers and dried by conventional means.
Preparation of p-tolylarsine A Schlenk flask containing 520 mg (13.7 mmol, ~2.5 equiv) of
lithium aluminum hydride was suspended in diethyl ether and cooled to –78 °C. Slowly, via
cannula, a solution of 1.274 g (5.38 mmol) of p-tolyldichloroarsine in diethyl ether was added. The
reaction stirred at –78 °C for 1 h, then gradually warmed to ambient temperature and stirred
overnight. The crude mixture was quenched with degassed water, and the solution was filtered via
cannula. Diethyl ether was removed by distillation under nitrogen. The product was slowly
sublimed from the crude reaction mixture at ambient temperature under nitrogen atmosphere (416
1
mg, 2.47 mmol, 46%). H NMR:  7.28 (d, J = 8 Hz, 2 H, C
6
H
4
CH
). C{ H}: δ 137.7 (s, C
), 21.0 (s, C CH ). MS calcd for C
3
), 6.85 (d, 8 Hz, 2 H, C
6
H
4
CH
3
3
),
),
13
1
3
1
.49 (s, 2 H, AsH
29.7 (s, C CH
2
), 2.03 (s, 3 H, C
), 126.0 (s, C
6
H
4
CH
3
6
H
4
CH ), 136.0 (s, C
3
6
H
4
CH
6
H
4
3
6
H
4
CH
3
6
H
4
3
7
9
H As: m/z 168.1.
Found: 168.8.
Preparation of (N
3
N)Zr(p-tolyl)AsH (2). A scintillation vial was charged with 41.4 mg (0.246
mmol) of p-tolylarsine, 112.1 mg (0.247 mmol) of 1, and ca 4 mL of toluene to give a deep
golden-orange solution. This solution stirred for twenty minutes, and then the toluene was
removed under reduced pressure. The crude reaction mixture was dissolved in pentane and
cooled to –20 °C to afford orange crystals after 3 d (110 mg, 0.178 mmol, 72%). Anal. Calcd for
1
C
22
H47AsN
4
Si
3
Zr Calc: C, 42.75; H, 7.67; N, 9.07. Found: C, 43.01; H, 7.55; N, 8.92. H NMR:
δ 7.71 (d, 8 Hz, 2 H, C
6
H
4
CH
3
), 6.97 (d, 8 Hz, 2 H, C
6
H
4
CH ), 3.38 (s, 1 H, AsH), 3.20 (t, J = 5
3
4

Hz, 6 H, CH
2
), 2.16 (s, 3 H, CH
C{ H}: δ 139.8 (s, C CH ), 135.3 (s, C
4.0 (s, CH ), 47.8 (s, CH ), 21.1 (s, C CH
75 ( = 367(9) M cm ).
.2 General procedure for catalytic hydroarsination reactions
3
), 2.13 (t, J = 5 Hz, 6 H, CH
CH ), 133.3 (s, C
), 1.2 (s, Si(CH
2
), 0.29 (s, 27 H, Si(CH
CH ), 129.1 (s, C
). UV-vis (toluene, max nm):
3
)
3
).
1
3
1
6
H
4
3
6
H
4
3
6
H
4
3
6
H
4
CH ),
3
6
3
2
2
6
H
4
3
3 3
)
-1
-1
2
A borosilicate NMR tube was charged with 0.1 mmol p-tolylarsine and 0.1 mmol alkene in the
presence of 5 mol % of 1 in benzene-d
6
solvent. The consumption of substrate to product was
1
1
monitored by H NMR spectroscopy. Conversions were determined by integration of H NMR
spectra.
3
. Results and Discussion
Prior work with 1 and primary arsines considered sterically bulky primary arsines for
dehydrocoupling reactivity to make new As–As bonds with concomitant formation of H .[7]
2
Although small, polar, unsaturated substrates could readily insert into a family of zirconium
arsenide derivatives, the arsines used in this report were too sterically encumbered for optimal
catalytic turnover.[7] For this work p-tolylarsine was chosen for its NMR handle and ease of
synthesis. The precursor p-tolyldichloroarsine was synthesized through modifications of literature
procedures (Scheme 1).[7, 23]
5

Scheme 1: Synthesis of p-tolylarsine
Reduction of p-tolyldichloroarsine afforded the desired arsine, albeit in low yields (<50%)
due to the high volatility of p-tolylarsine. Treatment of 1 with stochiometric p-tolylarsine in
toluene converts colorless 1 to the anticipated yellow zirconium-arsenido product,
(N
3
N)ZrAsHTol (2; N
3
N = N(CH
2
CH
2
NSiMe )
3–, Tol = p-tolune; eqn 3). The isolated yield of 2
3
3
1
is 72%, but observation of the reaction by H NMR spectroscopy reveals quantitative conversion
to 2, indicating that yield is a function of crystallization. The spectroscopic data for 2 is similar to
the broader family of triamidoamine-supported zirconium-arsenido and -phosphido derivatives.[7,
2
3
2, 24, 25] Of note, the arsenic proton and the p-toluene methyl protons resonate as a singlet at 
1
.38 and a triplet at  2.16 in the H NMR spectrum of 2, respectively.
6

(3)
Treatment of a 1:1 benzene-d
6
solution of p-tolylarsine and styrene with 5 mol % of 1
resulted in quantitative, immediate formation of 2 and only trace formation of the single activation
hydroarsination product, (Tol)AsHCH CH Ph, over a period of 24 hours (Table 1). It was
2
2
hypothesized that, as with hydrophosphination catalysis using 1, photolysis would enhance
reactivity.[21, 26] Running this reaction under irradiation in the visible, near ultraviolet, and in a
UV reactor all provided substantially improved conversions, and importantly, the control reaction
in strict darkness failed to give any turnover (Table 1). Likewise, reactions in the absence of 1
failed to give appreciable products under these conditions.
Table 1: Zirconium-catalyzed hydroarsination of styrene under different light sources.
Conditions: Twenty equiv. of p-tolylarsine, twenty equiv. of styrene, one equiv. of 1, ambient
1
temperature. Percent conversions were measured by H NMR spectroscopy.
Entry
Irradiation
visible
near UV
253.7 nm
ambient light
dark
% Conversion
1
2
3
4
5
44
48
54
trace
0
7

The increased catalytic activity of hydroarsination reactions run under ultraviolet or visible
irradiation suggests that hydroarsination may be operative via an analogous photoexcitation and
LMCT event as noted for catalytic hydrophosphination with 1 (vide infra).[21] Photocatalysis is
an attractive route to pnictanes because visible light irradiation suggests that sunlight could be
utilized, but more pragmatically, highly efficient photon sources such as LED bulbs can be utilized
rather than heating. While there was improvement in the conversion by movement to higher energy
sources, there was still good conversion with visible irradiation. A transition at 375 nm was
measured in the UV-vis spectrum of 2. Based on the similarity in energy and extinction coefficient
-1
-1
(
 = 367(9) M cm ) to the related phosphido derivative,[26] we tentatively assign this transition
as arsenic–zirconium charge transfer.
Previous studies on the catalytic hydrophosphination of styrene derivatives with 1 showed
selective formation of tertiary phosphine products, depending on reaction conditions.[27] In this
hydroarsination catalysis with 1, however, only secondary arsine products were detected (Table 1,
1
entries 1-3). Evidence for the secondary product comes from the H NMR spectra. For example,
1
the H NMR spectrum of (Tol)AsHCH
2
CH Ph contains an As–H triplet at  3.72. This catalysis is
2
the first example of a hydroarsination with a primary arsine and selectivity to form secondary
arsine products.
Additional styrene derivatives were considered for photocatalytic hydroarsination with 1
to make the desired secondary arsine products. Hydroarsination of styrene derivatives under visible
or ultraviolet irradiation shows comparable conversions for all styrene substrates, regardless of
electronic factors (Table 2, entries 1-3). There did appear to be slightly greater reactivity for
8

electron-rich styrenes, and a linear free-energy experiment was performed to test this preference.
Hammett competition experiments indeed showed greater reactivity of styrene derivatives bearing
electron-donating substituents, consistent with similar experimentation for catalytic
hydrophosphination. In that work, it was suggested that this reactivity was consistent with
insertion-based hydrophosphination.[26]
Table 2: Catalytic hydroarsination with 1. Conditions: Twenty equiv. of p-tolylarsine, twenty
equiv. of substrate, one equiv. of 1, near UV irradiation, ambient temperature. Percent
1
conversions are measured by H NMR spectroscopy.
Entry
a
Substrate
Product
% Conversion
5
6
0% (24 h)
2% (48 h)
b
4
5
4% (24 h)
1% (48 h)
c
4
5
6% (24 h)
8% (48 h)
d
100% (1 h)
9
2% (40 min)
8
8% (40 min,
dark)
e
f
1
1
00% (1 h)
00% (1 h)
g
-
No conversion
Conversions for the hydroarsination reactions of styrene derivatives as measured by NMR
spectoscopy are modest but consistent among all styrenes tested (Table 2, entries a–c). Reactions
9

run for 48 hours show a slight improvement in conversion to the hydroarsination product, but the
catalysis is sluggish overall. Heating the reactions under irradiation did not substantially impact
catalysis, as anticipated from previous studies on catalytic hydrophosphination.
Michael acceptors were excellent candidates for catalytic hydroarsination (Table 2, entries
d–f). These substrates proceeded smoothly to give high conversions to the secondary arsine
products after only one hour. Reactions with 1-hexene (Table 2, entry g) failed to provide
detectable levels of products after 48 hours, whereas 1-hexene with PhPH
50% conversion to the hydrophosphination product after 24 hours under irradiation.[26]
Many aspects of this system are similar to hydrophosphination catalysis with 1 including
the light-dependence, which is doubtlessly related to the similar electronic spectra of the
N)ZrER (E = P, As) derivatives in question. Studies on photocatalytic hydrophosphination with
found that photoexcitation promoted catalytic bond-formation by excitation to state with
2
and catalytic 1 provides
~
(N
3
1
significant Zr–P antibonding character and substantial Zr–P bond lengthening, which lead to the
hypothesis that insertion is facilitated by the weakening Zr–P bond under photolysis.[21] Given
the similar UV-vis absorbance spectra of both 2 and the analogous phosphido derivatives, it is
likely that a related charge transfer event occurs during photocatalytic hydroarsination, which
appears to accelerate hydrophosphination of styrene derivatives but is not sufficiently activated for
1
-hexene. The latter observation is consistent with greater reactivity of styrene substrates versus
simple alkenes in photocatalytic hydrophosphination using 1.
Nevertheless, there is a substantial difference in this reactivity. Control hydroarsination
reactions of the Michael acceptors in the dark provide similar if not the same conversions as
reactions run under irradiation. This observation harkens back to early work with trimaidoamine-
supported zirconium and arsines in which unsaturated substrates readily insert into the Zr–As bond
1
0

of the zirconium-arsenide compound (N
3
N)ZrAsHMes (Mes = 2,4,6-Me
3
C
6
2
H ).[7] The observed
increased activity of Michael acceptors over styrenes is consistent with previous study. The
indifference toward light for the catalytic hydroarsination with 1 of Michael acceptors as compared
to styrene derivatives that require photolysis argues for separate mechanisms in this catalysis. It
appears that the arsenido ligand of 2 is acting as a nucleophile for polar substrates but it can be
activated upon photolysis for insertion of less polar unsaturated molecules.
4
. Conclusions
Compound 1 is a pre-catalyst for hydroarsination of alkenes with a primary arise substrate
and provides exclusively secondary arsines with high selectivity for the anti-Markovnikov
product. These results are one in the limited set of catalytic hydroarsination reactions, and this is
the first report with primary arsines. An observed intermediate in the catalysis, (N
3
N)ZrAsHTol
(2), was independently prepared and spectroscopically characterized. The spectroscopic features
of 2 and light dependence in the hydroarsination of styrene substrates is similar to
hydrophosphination photocatalysis with 1. For Michael acceptors, the hydroarsination catalysis is
no longer light dependent. These observations suggest nucleophilic hydroarsination with activated
substrates and insertion-based hydroarsination for unactivated substrates, but only with Zr–As
bond activation under photolysis. This kind of divergent reactivity is to be important in further
developing metal-arsenido chemistry, and as is this new example of photocatalytic
heterofunctionalization.
Acknowledgment
This work was supported by the US National Science Foundation (CHE-1565658).
Dedication
1
1

To Prof. William Jones, a patient teacher and thoughtful scientist, on the occasion of his 65th
birthday.
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[
[
(
1
3

TOC graphic
1
4

Synopsis: A simple zirconium compound catalyzed the hydroarsination of alkynes with primary arsines,
which appears to have insertion or nucleophilic behavior based on the unsaturated substrate.
1
5