Neutral and Cationic Zirconium Complexes Bearing Multidentate Aminophenolato Ligands for Hydrophosphination Reactions of Alkenes and Heterocumulenes

Article abstract of DOI:10.1021/acs.inorgchem.7b02248

Zirconium complexes supported by multidentate aminophenolato ligands were synthesized and characterized. The catalytic activities of neutral zirconium complexes and their cationic derivatives in the hydrophosphination of alkenes as well as heterocumulenes have been investigated and compared. Neutral complex 1 bearing a multidentate amino mono(phenolato) ligand exhibited high activity in hydrophosphination of simple alkenes, and anti-Markovnikov products were obtained in 37-94% yields at room temperature. Cationic species generated in situ from complex 3 stabilized by a bis(phenolato) ligand were found to be more active for hydrophosphination of heterocumulenes, i.e., carbodiimides and isocyanates, and gave phosphaguanidines and phosphaureas in 67-93% yields. The Lewis acidity and coordination space of metal centers are modified through changes in the ligand structure, which is found to significantly influence catalytic activity. These complexes are among the most active group 4 metal-based catalysts for hydrophosphination reactions.

Full text of DOI:10.1021/acs.inorgchem.7b02248

Article
pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Neutral and Cationic Zirconium Complexes Bearing Multidentate
Aminophenolato Ligands for Hydrophosphination Reactions of
Alkenes and Heterocumulenes
Yu Zhang, Liye Qu, Yaorong Wang, Dan Yuan,* Yingming Yao,* and Qi Shen
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Dushu
Lake Campus, Soochow University, Suzhou 215123, People’s Republic of China
S
* Supporting Information
ABSTRACT: Zirconium complexes supported by multi-
dentate aminophenolato ligands were synthesized and
characterized. The catalytic activities of neutral zirconium
complexes and their cationic derivatives in the hydro-
phosphination of alkenes as well as heterocumulenes have
been investigated and compared. Neutral complex 1 bearing a
multidentate amino mono(phenolato) ligand exhibited high
activity in hydrophosphination of simple alkenes, and anti-
Markovnikov products were obtained in 37−94% yields at
room temperature. Cationic species generated in situ from
complex 3 stabilized by a bis(phenolato) ligand were found to
be more active for hydrophosphination of heterocumulenes,
i.e., carbodiimides and isocyanates, and gave phosphaguanidines and phosphaureas in 67−93% yields. The Lewis acidity and
coordination space of metal centers are modified through changes in the ligand structure, which is found to significantly influence
catalytic activity. These complexes are among the most active group 4 metal-based catalysts for hydrophosphination reactions.
intramolecular hydroamination reactions.8 As a continuation of
our interest in group 4 metal catalyzed hydroelementation
INTRODUCTION
■
Phosphorus-containing compounds are widely used in the
chemical and biological industries.1 The hydrophosphination
reactions, a study of neutral and cationic zirconium complexes
in catalyzing hydrophosphination reactions was conducted and
reaction, i.e., the addition of a P−H bond to C−C unsaturated
compared. Neutral zirconium trialkyl complexes were found to
be more active in catalyzing hydrophosphination of simple
alkenes, while cationic species showed superior activity in
bonds, is a 100% atom-economical route to construct C−P
bonds and has gained great attention in the past few decades.2
Since the first metal catalysts for hydrophosphination reported
in 1990,3 various catalytic systems involving late-transition-
hydrophosphination of heterocumulenes.
metal,2i,h lanthanide,2b and main-group2k elements have been
designed and studied. Some of them suffer from certain
limitations, such as low tolerance to functional groups (e.g.,
lanthanide complexes),4 high cost (e.g., late-transition-metal
complexes),2f,3,5 and requirement of excess phosphine (e.g., Cu
complexes).6 Although group 4 metal complexes have shown
good activity in hydroelementation reactions, e.g., hydro-
amination, studies on their application in hydrophosphination
are limited.7 Waterman et al. reported triamidoamine-
supported zirconium complexes which catalyzed hydrophosphi-
nation of primary phosphines with alkenes with high activity7d,e
and hydrophosphination of secondary phosphines with alkynes
and carbodiimides with moderate activity.7c Le Gendre et al.
reported Ti(II)-catalyzed 1,4-hydrophosphination of 1,3-dienes,
which however showed no activity for alkynes.7b Zwitterionic
titanium complexes reported by Mindiola et al. catalyzed
hydrophosphination of diphenylacetylene and gave a mixture of
E and Z isomers in 73% yield.7a
RESULTS AND DISCUSSION
■
Synthesis and Characterization of Zirconium Com-
plexes. Amine-bridged bis(phenolato) ligands are a promising
class of ancillary ligands that well stabilize metal centers.9
Moreover, ligand modifications can be easily achieved through
changes in substituents on the nitrogen atom and/or aromatic
rings, which influences complex structures and catalytic
activities. In this study, one of the phenolate groups was
etherified, giving rise to mono(phenolato) ligands bearing
multiple coordination sites. Ligand precursors were prepared
via modified literature procedures.10 Zirconium trialkyl
complexes 1 and 2 were synthesized through a straightforward
metathesis method by treating ligand precursors L1H and L2H
with ZrBn4, which were isolated in 72% and 45% yields,
respectively (Scheme 1). Zirconium dialkyl complexes 3−6
Our group has reported that cationic zirconium complexes
are more active than their neutral analogues in inter- and
Received: September 5, 2017
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b02248
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Scheme 1. Synthesis of Zirconium Complexes Bearing Multidentate Phenolato Ligands
were prepared according to literature methods for comparison
purposes.8,11
recorded over the range of 10−60 °C in C6D6 to elucidate
whether there is fluxional behavior (Supporting Information).
As temperature changes, the proportion of trans−cis
configurations changes only slightly, while all signals remain
sharp. This finding implies that there is limited fluxionality of
complex 1 in solution. A more fluxional solution behavior of
complex 2 was observed, as methylene protons give rise to
broad signals. In addition to cis−trans isomerization, a
coordination−dissociation process involving the OMe group
as a result of one less donor in ligand L2 may occur in solution.
The solid-state structure of complex 1 (depicted in Figure 2)
shows that the zirconium center is six-coordinate, ligated by
three benzyl groups and two N atoms and one O atoms from
ligand L1. The coordination geometry is distorted octahedral
with atoms N2 and C50 occupying the axial positions (N2−
Zr1−C50 175.85°), and atoms Zr1, N1, O1, C43, and C36 (the
sum of angles N1−Zr1−O1, O1−Zr1−C43, C43−Zr1−C36,
and C36−Zr1−N1 is 359.06°) are nearly coplanar. A cis-
chelating mode of L1 is observed, as supported by the N1−
Zr1−O1 angle of 76.08° and N2−Zr1−O1 angle of 92.57°.
The OCH3 group does not coordinate to the metal center, as
evidenced by the longer distance between Zr1 and O2
(5.5893(2) Å) in comparison to the sum of atomic radii (rZr
1
The identity of complex 1 was confirmed by H and 13C
NMR spectroscopy, elemental analyses and X-ray diffraction
1
analysis. In the H NMR spectrum, all methylene protons
become diastereotopic and give rise to doublets/multiplets in
the range of 4.8−2.4 ppm. Signals of the N(CH3)2 group
appear as two singlets at 2.17 and 1.59 ppm, in contrast to the
singlet in ligand L1, suggesting coordination of the N(CH3)2
group to the metal center. The OCH3 group was found
resonating at 3.39 ppm as a sharp singlet. Moreover, in addition
to the major set of signals, a smaller set of signals with an
integration consistent with the stoichiometric structure of
complex 1 was observed, which indicates that two isomers, i.e.,
cis and trans configurations, may exist in solution (Figure 1).10a
Variable-temperature 1H NMR spectra of complex 1 were
Figure 1. Possible cis and trans configurations of complex 1.
B
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4, and 6), with the exception of complex 5 (90% yield) (entry
5). Lowering the catalyst loading to 5 mol % resulted in a lower
yield of 60% (entry 1). The activity difference between
zirconium tribenzyl and dibenzyl complexes may be due to
the fact that more alkyl groups per zirconium center in the
former will participate in a metathesis reaction with HPPh2
(vide infra). The fact that 15 mol % of complex 3 led to a
higher yield of 96% supported this hypothesis (entry 3). It is
noteworthy that 7.5 mol % of ZrBn4 bearing the same number
of benzyl groups resulted in only 72% yield, proving that the
multidentate phenolato ligand contributes to catalytic activity
improvement through adjustment of electronic and steric
properties. The higher catalytic activity of complex 5 carrying
an [ONO] tridentate bis(phenolato) ligand may be ascribed to
more coordination sites for substrates as a result of one less
donor in ligand L5, which is consistent with previous findings
from Zr-catalyzed hydroamination reactions.8
Addition of [Ph3C][B(C6F5)4] (TB) led to decreased yields
of 56% and 60%, respectively (Table 1, entries 7 and 8), which
is different from observations that cationic complexes are more
active than their neutral counterparts in hydroamination
reactions.8 This may be due to the fact that the Zr−P bond
formed from the Zr-alkyl complex and PPh2H is stronger for
cationic species, which inhibits the subsequent insertion of
alkene into Zr−P bonds (vide infra). Similar phenomena have
been reported for cationic group 3 metal catalysts.12 With the
neutral complex 1, different solvents were also screened
(entries 9 and 10), and neat conditions were found to be
optimal. In the absence of Zr complex, a low yield of 48% was
obtained (entry 11).
Under optimal conditions, a series of alkenes were studied
and tertiary phosphines formed as anti-Markovnikov addition
products in 37−94% yields (Table 2). Styrene derivatives
bearing either electron-donating or -withdrawing groups at
ortho, meta, or para positions reacted smoothly at room
temperature and gave tertiary phosphines in 82−93% yields
(entries 1−6), indicating good functional group tolerance of
this catalytic system. 2- and 4-vinylpyridine were converted to
tertiary phosphines in 92 and 87% yields, respectively (entries 7
and 8). A low yield of 37% was obtained with 2-methylstyrene
due to steric reasons (entry 9). The transformation of
phenylacetylene was less efficient, which resulted in 40%
yield, albeit in good Z/E selectivity of 96/4 (entry 10). In
comparison, a much lower yield of 6% was obtained with ZrBn4
(entry 10). Although many catalytic systems have been
reported to catalyze this reaction,13 examples operative at
room temperature are rare, which involve iron complexes
reported by Webster et al. and ytterbium and calcium
complexes by Cui et al.4c,14 A comparison of Zr complex 1
with literature reports showed higher activity for heterocycle-
containing alkenes, i.e., 2-vinylpyridine (7p) and 4-vinyl-
pyridine (7q), which generally required higher reaction
temperature and/or prolonged reaction time.4c,14 For some
substrates, i.e., 1-methoxy-4-vinylbenzene (7n) and 1-chloro-4-
vinylbenzene (7j), higher yields were also obtained in the
presence of zirconium complex 1. Trialkyl zirconium complexes
represent the first group 4 metal based catalysts capable of
promoting hydrophosphination reactions of secondary phos-
phines at room temperature.
Figure 2. Molecular structure of 1·C7H8 showing 30% probability
ellipsoids. Hydrogen atoms are omitted for clarity. Selected bond
lengths (Å) and bond angles (deg): Zr1−O1 1.995(2), Zr1−N1
2.535(3), Zr1−N2 2.573(3), Zr1−C36 2.326(4), Zr1−C43 2.295(4),
Zr1−C50 2.296(4); O1−Zr1−N1 76.07(9), O1−Zr1−N2 92.58(10),
O1−Zr1−C36 165.10(12), O1−Zr1−C43 98.15(14), O1−Zr1−C50
90.03(13), N1−Zr1−N2 70.74(9), N1−Zr1−C36 89.12(11), N1−
Zr1−C43 151.69(13), N1−Zr1−C50 106.82(12), N2−Zr1−C36
83.96(13), N2−Zr1−C43 82.02(14), N2−Zr1−C50 175.85(12),
C36−Zr1−C43 95.72(15), C36−Zr1−C50 92.70(15), C43−Zr1−
C50 100.81(16).
= 2.16 Å, rO = 1.520 Å), which is consistent with Zn, Mg, and
Ti complexes of similar ligands.10
Catalytic Hydrophosphination Reactions of Alkenes.
To study the catalytic activities of complexes 1−6, a
hydrophosphination reaction of styrene (7a) and diphenyl-
phosphine (8) was first tested (Table 1). Under mild
conditions (neat, 25 °C, 40 h), reactions catalyzed by 10 mol
% of zirconium tribenzyl complexes 1 and 2 gave the anti-
Markovnikov product 9a in 94% and 90% yields (entries 1 and
2), respectively, which are in general higher than those of
dibenzyl zirconium complexes 3−6 (61−65% yields) (entries 3,
Table 1. Intermolecular Hydrophosphination of Styrene
(7a) with Diphenylphosphine (8) Catalyzed by Complexes
a
1−6
b
entry
cat.
solvent
conversn (%)
c
d
1
1
2
3
4
5
6
none
none
none
none
none
none
none
none
toluene
PhCl
none
94 (90, 60 )
90
2
e
3
64 (96)
4
65
90
61
56
60
40
65
48
5
6
7
1 + TB
3 + TB
1
8
9
10
11
1
none
a
Conditions unless specified otherwise: styrene (7a; 114 μL, 1 mmol),
diphenylphosphine (8; 174 μL, 1 mmol) precatalyst 1−6 (0.1 mmol,
In addition to aromatic alkenes, hydrophosphination
reactions of aliphatic alkenes were also explored, including
dienes and acrylates (Table 3). 1,4-Addition reactions of dienes
occurred exclusively, which were less efficient than that of
10 mol %), [Ph3C][B(C6F5)4] (TB; 0.092 g, 0.1 mmol) if necessary,
b
1
solvent (2 mL) if necessary, 25 °C, 40 h. Determined by H NMR
c
d
e
spectroscopy. Isolated yield. 5 mol % catalyst loading. 15 mol %
catalyst loading.
C
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Table 2. Intermolecular Hydrophosphination Reactions of Aromatic Alkenes and Alkynes with Diphenylphosphine Catalyzed
a
by Complex 1
a
b
c
Conditions: alkene 7 (0.5 mmol), diphenylphosphine (8; 87 μL, 0.5 mmol), complex 1 (0.045 g, 0.05 mmol), neat, 25 °C, 40 h. Isolated yield. Z/
d
E ratio 96/4, determined by 31P NMR spectroscopy. 7.5 mol % of ZrBn4.
styrene, as temperature elevation was required (entries 1 and
2). Moreover, a steric effect was obvious, as reaction time
extension was needed for substrate 7u bearing a bulky hexyl
substituent. Methyl acrylate (7v) reacted smoothly with HPPh2
at room temperature, and the reaction was complete within 12
h with 85% isolated yield (entry 3). In comparison, slightly
lower yields were obtained with complexes 2−6 (entry 3).
Reactions of other aliphatic alkenes, e.g. hexene, 1,3-cyclo-
hexadiene, and norbornene, did not proceed; however, these
reactions worked in the presence of a triamidoamine Zr
complex or Ca complex.7d,15
Catalytic Hydrophosphination Reactions of Carbodii-
mides. Metal catalyst systems,16 involving alkali-metal,16a and
alkaline-earth-metal,16b,h rare-earth,16c,f,g,17 and actinide com-
plexes,16d,e,i have been developed to catalyze hydrophosphina-
tion reactions of carbodiimides. The only example of a
zirconium catalyst was reported by Waterman et al., which
led to phosphaguanidine formation in moderate yields of 53−
75%.7c Reaction of N,N′-diisopropylcarbodiimide (10a) and
D
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reaction and generated product 11a in a low yield of 23%
(entry 10). Nearly no conversion was detected in the absence
of any catalyst (entry 11).
Table 3. Intermolecular Hydrophosphination Reactions of
Aliphatic Alkenes with Diphenylphosphine Catalyzed by
Complex 1
a
Aliphatic and aromatic carbodiimides were converted into
the corresponding phosphaguanidines in 85% and 82% yields
(Table 5), respectively. A higher temperature was required for
Table 5. Intermolecular Hydrophosphination Reactions of
Carbodiimides with Diphenylphosphine Catalyzed by
a
Complex 3
a
Conditions: alkene 7 (0.5 mmol), diphenylphosphine (8; 87 μL, 0.5
b
mmol), complex 1 (0.045 g, 0.05 mmol), neat. Isolated yield. S8
(0.018 g, 0.07 mmol) was added to facilitate the purification on silica
c
gel. Z/E ratio 3/1 determined by 31P NMR spectroscopy.
diphenylphosphine (8) was examined with complexes 1−6
(Table 4). A trace amount of the product formed in the
a
Conditions: 10 (0.5 mmol), diphenylphosphine (87 μL, 0.5 mmol), 3
(0.040 g, 0.05 mmol), [Ph3C][B(C6F5)4] (TB; 0.046 g, 0.05 mmol),
PhCl (2 mL). Isolated yield.
b
Table 4. Intermolecular Hydrophosphination of
Diisopropylmethanediimine (10a) with Diphenylphosphine
a
(8) Catalyzed by Complexes 1−6
the reaction of dicyclohexylcarbodiimide (entry 1) in
comparison to that for diphenylcarbodiimide (entry 2). No
reaction took place at room temperature, making zirconium
complexes less active than alkali-metal and alkaline-earth-metal
complexes.16a,b,h
b
entry
cat.
solvent
conversn (%)
1
1
3
PhCl
PhCl
PhCl
PhCl
PhCl
none
PhCl
PhCl
PhCl
PhCl
PhCl
11
trace
85
Catalytic Hydrophosphination Reactions of Isocya-
nates. Studies on hydrophosphinaton reactions of isocyanates
are relatively rare in comparison to those of alkenes and
carbodiimides, as only a few catalysts based on actinide,16d,e,i
iron,18 and rare-earth metals16 have been reported. No Zr-
catalyzed hydrophosphinaton of isocyanates have been
reported. Phenyl isocyanate (12a) was treated with diphenyl-
phosphine (8) in the presence of zirconium trialkyl complex 1
and dialkyl complex 3 at 60 °C, respectively, and moderate
yields of 70% and 58% were obtained (Table 6, entries 1 and
2). Addition of TB led to increased yields of 81% and 93%,
respectively (entries 3 and 4). Similar to reactions of
carbodiimides, cationic species showed higher activity, and
the combination of complex 3 and TB gave the best result
(entries 3 and 8−11). A mixture of complex 1 and
[Ph3C][B(C6F5)4] (2 equiv) was employed to catalyze the
hydrophosphination of phenyl isocyanate, and a lower yield of
73% yield was obtained (entry 3). This may be due to the fact
that strong Lewis acidities of dicationic species lead to strong
binding of substrates, which inhibits the subsequent insertion of
alkene into Zr−P bonds. Different conditions (neat, 5 mol %
catalyst loading, or room temperature) were screened, and the
optimal result was obtained in PhCl at 60 °C in the presence of
10 mol % of catalyst (entry 3). It is noteworthy that, at room
temperature, a good yield of 82% (entry 7) was obtained,
revealing that zirconium complexes are more active than
actinide and rare-earth-metal catalysts.16d,e,17 Low yields were
detected with either TB alone or no catalyst (entries 12 and
13).
2
3
1 + TB
2 + TB
3 + TB
3 + TB
4 + TB
5 + TB
6 + TB
TB
4
85
c
5
90 (88)
6
52
82
75
77
23
3
7
8
9
10
11
none
a
Conditions: diisopropylmethanediimine (10a; 154 μL, 1 mmol),
diphenylphosphine (8; 174 μL, 1 mmol), precatalyst 1−6 (0.1 mmol,
10 mol %), [Ph3C][B(C6F5)4] (TB; 0.092 g, 0.1 mmol) if necessary,
b
PhCl (2 mL) if necessary, 100 °C, 15 h. Determined by 31P NMR
c
spectroscopy. Isolated yield.
presence of either neutral zirconium tribenzyl complex 1 or
dibenzyl complex 3 (entries 1 and 2). However, cationic species
generated in situ from neutral complexes and TB efficiently
catalyzed the hydrophosphination of carbodiimide (entries 3
and 5). Although the Zr−P bond is stronger for cationic
species, the insertion of heterocumulenes is feasible, possibly
due to the formation of a chelating phosphaguanidine ligand.
The interplay between suitable Lewis acidity and coordination
space of metal centers influences catalytic activities. On
comparison of complexes 1−6, cationic complexes derived
from zirconium dibenzyl complex 3 bearing an [ONNO]-type
tetradentate bis(phenolato) ligand showed the highest activity
in PhCl (entries 3−9). [Ph3C][B(C6F5)4] alone catalyzed the
E
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Table 6. Intermolecular Hydrophosphination Reactions of
Phenyl Isocyanate (12a) with Diphenylphosphine (8)
Catalyzed by Zirconium Complexes
Table 7. Intermolecular Hydrophosphination Reactions of
Isocyanates 12 with Diphenylphosphine 8 Catalyzed by
Complex 3
a
a
b
entry
cat.
solvent
yield (%)
1
1
3
PhCl
PhCl
PhCl
PhCl
none
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
PhCl
70
58
2
c
3
1 + TB
3 + TB
3 + TB
3 + TB
3 + TB
2 + TB
4 + TB
5 + TB
6 + TB
TB
81 (73)
d
4
93 (90)
5
69
e
6
79
f
7
82
8
74
71
74
88
40
9
10
11
12
13
f
none
48
a
Conditions unless specified otherwise: phenyl isocyanate (12a; 54
μL, 0.5 mmol), diphenylphosphine (8; 87 μL, 0.5 mmol), 3 (0.05
mmol, 0.040 g), [Ph3C][B(C6F5)4] (TB; 0.046 g, 0.05 mmol) if
b
necessary, PhCl (2 mL), 60 °C, 24 h. Determined by 31P NMR
c
d
e
spectroscopy. 0.2 mmol of TB. Isolated yield. 5 mol % catalyst
f
loading. Room temperature.
Aryl isocyanates bearing different substituents were tested
under optimized conditions (Table 7). Both electron-with-
drawing and -donating groups were tolerated in this catalytic
system, and good yields of 83−93% were obtained (entries 1−
3). Reaction of 1-naphthyl isocyanate (12e) afforded the
desired product phosphaurea 13e in a moderate yield of 71%,
possibly due to steric reasons (entry 4). Aliphatic isocyanates,
i.e., propyl isocyanate and cyclopentyl isocyanate, were also
converted into the respective phosphaureas 13f,g in 87 and
67% yields, respectively (entries 5 and 6), showing a broad
substrate scope of this Zr-based catalytic system.
a
Conditions unless specified otherwise: 12 (0.5 mmol), diphenyl-
phosphine (8; 87 μL, 0.5 mmol), 3 (0.040 g, 0.05 mmol),
[Ph3C][B(C6F5)4] (TB; 0.046 g, 0.05 mmol), PhCl (2 mL). Isolated
yield. In PhBr-d5 (0.7 mL), determined by H NMR spectroscopy.
b
c
1
EXPERIMENTAL SECTION
■
General Considerations. All operations of air- or moisture-
sensitive reactions were carried out under a nitrogen atmosphere using
standard Schlenk glassware or glovebox techniques. Toluene and
hexane were dried by refluxing over Na wire and distilled prior to use.
PhCl, PhBr-d5, and CDCl3 were distilled from CaH2 and stored under
CONCLUSION
19
■
argon. ZrBn4 and complexes 3−6 were synthesized according to
methods reported in the literature.8,11 1H, 13C, and 31P NMR spectra
were recorded on a Bruker AVANCE III HD-400 spectrometer. X-ray
crystallographic data were acquired using an AXS D8 X-ray
diffractometer. Elemental analysis data were obtained with an EA-
1110 instrument.
In summary, zirconium complexes bearing multidentate
aminophenolato ligands have been prepared to catalyze
hydrophosphination reaction of alkenes and heterocumulenes.
Catalytic activities were significantly influenced by modification
of ancillary ligands. For hydrophosphination of simple alkenes,
trialkyl zirconium complex 1 bearing a multidentate amino
mono(phenolato) ligand was found to be more active than
dialkyl zirconium complexes 3−6 stabilized by bis(phenolato)
ligands. Various alkenes with different substituents reacted with
HPPh2 and formed tertiary phosphines in 37−94% yields at
room temperature. In comparison, cationic species generated in
situ from complex 3 were found to be more active for the
hydrophosphination of heterocumulenes, i.e., carbodiimides
and isocyanates, and gave phosphaguanidines and phosphaur-
eas in 67−93% yields. Through ligand structure modification,
the Lewis acidity and coordination space of metal centers are
adjusted, which is found to significantly influence catalytic
activity. These complexes are among the most active group 4
metal based catalysts for hydrophosphination reactions. Further
studies on the group 4 metal complexes and their catalytic
activities are ongoing in our laboratory.
Preparation of Complex 1. A flame-dried 50 mL Schlenk tube
was charged with ZrBn4 (0.91 g, 2 mmol) and toluene (10 mL). A
solution of L1H1 (1.08 g, 2 mmol) in toluene (20 mL) was added
dropwise at room temperature. A yellow solid precipitated out during
this period. After the mixture was stirred overnight, it was heated until
the solid was mostly dissolved and centrifuged. The saturated solution
was left in the Schlenk flask, and after a few days, yellow crystals
formed from the solution at room temperature. Crystals were
collected, washed with toluene (3 × 2 mL), and dried (1.30 g, 1.4
mmol, 72%). Complex 1 is sensitive to both air and moisture and can
1
be stored under inert conditions for months. H NMR (400 MHz,
C6D6): δ 7.51 (d, 1H, J = 2.35 Hz, ArH), 7.49 (d, 1H, J = 2.51 Hz,
ArH), 7.33 (m, 8H, ArH), 7.12 (m, 2H, ArH), 6.94 (m, 3H, ArH),
6.82 (m, 3H, ArH), 6.60 (d, 1H, J = 2.28 Hz, ArH), 4.83 (d, 1H, J =
13.13 Hz, CH2N), 3.71 (d, 1H, J = 13.13 Hz, CH2N), 3.37 (s, 3H,
OCH3), 3.25−3.22 (m, 1H, CH2N), 3.13 (t, 1H, CH2N), 3.03−2.96
(m, 1H, CH2N), 2.93 (s, 2H, CH2Ar), 2.84 (s, 2H, CH2Ar), 2.80−2.73
(m, 2H, CH2N), 2.43 (t, 1H, CH2N), 2.17 (s, 3H, NCH3), 1.90 (s,
F
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Article
2H, CH2Ar), 1.75 (s, 9H, C(CH3)3), 1.59 (s, 3H, NCH3), 1.37 (s, 9H,
C(CH3)3), 1.35 (s, 9H, C(CH3)3), 1.11 (s, 9H, C(CH3)3). 13C{1H}
NMR (100 MHz, CDCl3): 157.8, 155.8, 152.9, 148.1, 145.3, 142.6,
141.9, 136.5, 131.2, 128.3, 126.7, 125.9, 125.8, 125.2, 125.1, 123.8,
123.6, 121.4, 120.3, 120.1 (Ar-C), 63.5 (Ar-CH2N), 59.9 (Ar-CH2N),
58.7 (OCH3), 54.3 (NCH2), 50.2 (NCH2), 47.3 (NCH3), 45.4
(NCH3), 35.4 (C(CH3)3), 34.7 (C(CH3)3), 34.4 (C(CH3)3), 31.7
(C(CH3)3), 31.5 (C(CH3)3), 31.4 (C(CH3)3), 30.6 (C(CH3)3). Anal.
Calcd for C56H78N2O2Zr: C, 74.53; H, 8.71; N, 3.10. Found: C, 75.44;
H, 8.39; N, 2.77.
(100 MHz, CDCl3): 162.4, 160.0, 138.6, 138.5, 133.0, 132.8, 130.6,
130.5, 128.8, 128.7, 128.6, 128.0, 127.9, 124.2, 115.6, 115.3 (Ar-C),
29.0, 28.9 (PCH2), 25.9 (CH2). MS: calcd m/z 309.1208 for C20H19FP
[M + H]+, found 309.1197.
(2-Chlorophenethyl)diphenylphosphane (9c).20b 9c was prepared
from 7c (64 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 82% yield (0.133 g). 1H NMR (400 MHz, CDCl3): δ 7.40−7.36 (m,
4H, ArH), 7.25−7.21 (m, 7H, ArH), 7.09−7.00 (m, 3H, ArH), 2.78−
2.71 (m, 2H, CCH2C), 2.29−2.25 (m, 2H, CCH2P). 31P{1H} NMR
(162 MHz, CDCl3): −15.54.
Preparation of Complex 2. A flame-dried 50 mL Schlenk tube
was charged with ZrBn4 (0.91 g, 2 mmol) and toluene (10 mL), and a
solution of L2H1 (1.05 g, 2 mmol) in toluene (20 mL) was added
dropwise at room temperature. The solution turned from orange to
yellow during this period. After the mixture was stirred overnight, it
was concentrated to around 5 mL and centrifuged. The saturated
solution was left in the Schlenk flask, and after a few days, yellow
crystals formed from the solution at −30 °C. Crystals were collected,
washed with toluene (3 × 2 mL), and dried (0.80 g, 0.9 mmol, 45%).
Complex 2 is sensitive to both air and moisture and can be stored
(2-Bromophenethyl)diphenylphosphane (9d). 9d was prepared
from 7d (63 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 81% yield (0.149 g). 1H NMR (400 MHz, CDCl3): δ 7.41−7.37 (m,
5H, ArH), 7.25−7.24 (m, 6H, ArH), 7.10−7.09 (m, 2H, ArH), 6.92−
6.96 (m, 1H, ArH), 2.78−2.72 (m, 2H, CCH2C), 2.29−2.25 (m, 2H,
CCH2P). 31P{1H} NMR (162 MHz, CDCl3): −15.43. 13C{1H} NMR
(100 MHz, CDCl3): 142.2, 142.0, 138.6, 138.4, 133.1, 132.0, 132.9,
130.5, 128.9, 128.7, 128.6, 128.0, 127.7, 124.3 (Ar-C), 33.1, 32.9
(PCH2), 28.8, 28.7 (CH2). MS: calcd m/z 369.0408 for C20H19BrP [M
+ H]+, found 369.0406.
1
under inert conditions for months. H NMR (400 MHz, CDCl3): δ
(3-Fluorophenethyl)diphenylphosphane (9e). 9e was prepared
from 7e (60 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 84% yield (0.129 g). 1H NMR (400 MHz, CDCl3): δ 7.38−7.34 (m,
5H, ArH), 7.27−7.26 (m, 5H, ArH), 7.15−7.09 (m, 1H, ArH), 6.86−
6.76 (m, 3H, ArH), 2.66−2.60 (m, 2H, CCH2C), 2.28−2.24 (m, 2H,
CCH2P). 31P{1H} NMR (162 MHz, CDCl3): −16.1. 13C{1H} NMR
(100 MHz, CDCl3): 164.3, 161.9, 145.4, 145.3, 145.1, 138.5, 138.4,
133.0, 132.8, 130.0, 128.9, 128.7, 124.0, 115.3, 115.1, 113.2, 113.0 (Ar-
C), 32.2, 32.0 (PCH2), 30.2, 30.0 (CH2). MS: calcd m/z 309.1208 for
C20H19FP [M + H]+, found 309.1198.
7.88 (d, 2H, J = 2.60 Hz, ArH), 7.32−7.37 (m, 2H, ArH), 6.97−6.95
(m, 7H, ArH), 6.85−6.76 (m, 3H, ArH), 6.78−6.68 (m, 9H, ArH),
3.76 (s, 3H, OCH3), 2.95 (s, 4H, CCH2N), 2.68 (s, 6H, ArCH2), 2.29
(d, 3H, NCH2C), 1.68 (s, 9H, o-C(CH3)3), 1.58 (s, 9H, o-C(CH3)3),
1.54(s, 1H, CCH2C), 1.50(s, 1H, CCH2C), 1.32 (s, 9H, p-C(CH3)3)
1.29 (s, 9H, p-C(CH3)3), 1.26 (m, 2H, CCH2C), 0.70 (s, 3H, CCH3).
13C{1H} NMR (100 MHz, CDCl3, CDCl3): 156.5, 153.8, 148.7, 141.9,
141.6, 138.0, 136.2, 128.9, 128.8, 128.7, 128.6, 128.4, 128.1, 126.3,
125.8, 125.1, 124.1, 120.7 (Ar-C), 66.4 (Ar-CH2N), 58.8 (Ar-CH2N),
55.8 (OCH3), 53.1 (NCH2C), 36.3 (C(CH3)3), 35.4 (C(CH3)3), 34.7
(C(CH3)3), 34.5 (C(CH3)3), 33.3 (C(CH3)3), 31.9 (C(CH3)3), 31.5
(C(CH3)3), 30.6 (C(CH3)3), 23.2 (CCH2C), 20.2 (CCH2C), 14.5
(CH3). Anal. Calcd for C56H77NO2Zr: C, 75.79; H, 8.75; N, 1.58.
Found: C, 73.73; H, 8.07; N, 0.969.
(3-Chlorophenethyl)diphenylphosphane (9f).20b 9f was prepared
from 7f (64 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 82% yield (0.133 g). 1H NMR (400 MHz, CDCl3): δ 7.37−7.33 (m,
4H, ArH), 7.25−7.24 (m, 6H, ArH), 7.07−7.06 (m, 3H, ArH), 6.95−
6.93 (m, 1H, ArH), 2.63−2.57 (m, 2H, CCH2C), 2.27−2.23 (m, 2H,
CCH2P). 31P{1H} NMR (162 MHz, CDCl3): −16.05.
General Procedure for Hydrophosphination Reactions. For
hydrophosphination of alkenes, a flame-dried 5 mL Schlenk tube was
charged with complex 1 (0.045 g, 0.05 mmol), diphenylphosphine (87
μL, 0.5 mmol), and alkene 7 (0.5 mmol). The resulting mixture was
stirred neat at 25 °C for 40 h unless otherwise specified. After the
reaction, the crude products were purified by column chromatography
(petroleum ether/ethyl acetate 200/1, silica gel). S8 (0.018 g, 0.7
mmol) was added in the case of products 9w−y before column
chromatography to facilitate purification. Isolated products were
(3-Bromophenethyl)diphenylphosphane (9g).20b 9g was prepared
from 7g (65 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 81% yield (0.153 g). 1H NMR (400 MHz, CDCl3): δ 7.37−7.32 (m,
4H, ArH), 7.25−7.20 (m, 8H, ArH), 7.04−6.97 (m, 2H, ArH), 2.62−
2.56 (m, 2H, CCH2C), 2.26−2.26 (m, 2H, CCH2P). 31P{1H} NMR
(162 MHz, CDCl3): −15.89.
(4-Fluorophenethyl)diphenylphosphane (9h).4c 9h was prepared
from 7h (60 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 82% yield (0.126 g). 1H NMR (400 MHz, CDCl3): δ 7.46−7.42 (m,
4H, ArH), 7.34−7.33 (m, 6H, ArH), 7.13−7.09 (m, 2H, ArH), 6.96−
6.92 (m, 2H, ArH), 2.73−2.66 (m, 2H, CCH2C), 2.36−2.32 (m, 2H,
CCH2P). 31P{1H} NMR (162 MHz, CDCl3): −16.26.
1
characterized by H and 31P NMR spectroscopy.
For hydrophosphination of heterocumulenes, a flame-dried 5 mL
Schlenk tube was charged with complex 3 (0.040 g, 0.05 mmol),
[Ph3C][B(C6F5)4] (TB; 0.046 g, 0.05 mmol), and PhCl (2 mL). The
solution was stirred for 5 min, and a color change from orange to
yellow was observed. Subsequently diphenylphosphine (87 μL, 0.5
mmol) and carbodiimide 10 (0.5 mmol) or isocyanate 12 (0.5 mmol)
were added. The resulting mixture was stirred at 100 °C for 15 h (for
carbodiimide unless otherwise specified) or 60 °C for 24 h (for
isocyanate). After the reaction, products were extracted by pentane
and dried under vacuum (11a−c) or purified by column
chromatography (petroleum ether/ethyl acetate 50/1, silica gel,
(4-Chlorophenethyl)diphenylphosphane (9i).20b 9i was prepared
from 7i (60 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 82% yield (0.133 g). 1H NMR (400 MHz, CDCl3): δ 7.37−7.33 (m,
4H, ArH), 7.25−7.24 (m, 6H, ArH), 7.14−7.12 (m, 2H, ArH), 7.00−
6.98 (m, 2H, ArH), 2.63−2.57 (m, 2H, CCH2C), 2.26−2.22 (m, 2H,
CCH2P). 31P{1H} NMR (162 MHz, CDCl3): −16.22.
(4-Bromophenethyl)diphenylphosphane (9j).20b 9j was prepared
from 7j (65 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 90% yield (0.166 g). 1H NMR (400 MHz, CDCl3): δ 7.45−7.41 (m,
4H, ArH), 7.34−7.28 (m, 8H, ArH), 7.13−7.06 (m, 2H, ArH), 2.71−
2.64 (m, 2H, CCH2C), 2.35−2.30 (m, 2H, CCH2P). 31P{1H} NMR
(162 MHz, CDCl3): −16.01.
1
13a−e). Isolated products were characterized by H and 31P NMR
spectroscopy.
Phenethyldiphenylphosphane (9a).4c 9a was prepared from 7a
(57 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil in 90%
yield (0.131 g). H NMR (400 MHz, CDCl3): δ 7.47−7.43 (m, 4H,
(2-Methylphenethyl)diphenylphosphane (9k).20a 9k was prepared
from 7k (65 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 90% yield (0.137 g). 1H NMR (400 MHz, CDCl3): δ 7.48−7.44 (m,
4H, ArH), 7.34−7.33 (m, 6H, ArH), 7.13−7.09 (m, 4H, ArH), 2.71−
2.65 (m, 2H, CCH2C), 2.31−2.27 (m, 2H, CCH2P), 2.17 (s, 3H,
CH3) 31P{1H} NMR (162 MHz, CDCl3): −15.40.
1
ArH), 7.35−7.33 (m, 6H, ArH), 7.29−7.25 (m, 2H, ArH), 7.19−7.16
(m, 3H, ArH), 2.75−2.69 (m, 2H, CCH2C), 2.38−2.34 (m, 2H,
CCH2P). 31P{1H} NMR (162 MHz, CDCl3): −15.87.
(2-Fluorophenethyl)diphenylphosphane (9b). 9b was prepared
from 7b (60 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 79% yield (0.122 g). 1H NMR (400 MHz, CDCl3): δ 7.49−7.45 (m,
4H, ArH), 7.35−7.34 (m, 6H, ArH), 7.19−7.14 (m, 2H, ArH), 7.05−
6.97 (m, 2H, ArH), 2.80−2.74 (m, 2H, CCH2C), 2.39−2.35 (m, 2H,
CCH2P). 31P{1H} NMR (162 MHz, CDCl3): −15.84. 13C{1H} NMR
(3-Methylphenethyl)diphenylphosphane (9l).20b 9l was prepared
from 7l (66 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 86% yield (0.131 g). 1H NMR (400 MHz, CDCl3): δ 7.39−7.35 (m,
4H, ArH), 7.26−7.24 (m, 6H, ArH), 7.10−7.06 (m, 1H, ArH), 6.90 (t,
G
DOI: 10.1021/acs.inorgchem.7b02248
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
3H, ArH), 2.64−2.58 (m, 2H, CCH2C), 2.30−2.26 (m, 2H, CCH2P),
2.23 (s, 3H, CH3) 31P{1H} NMR (162 MHz, CDCl3): −15.70.
(4-Methylphenethyl)diphenylphosphane (9m).4c 9m was prepared
from 7m (66 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 88% yield (0.134 g). 1H NMR (400 MHz, CDCl3): δ 7.45−7.43 (m,
4H, ArH), 7.32−7.31 (m, 6H, ArH), 7.08−7.03 (m, 4H, ArH), 7.19−
7.16 (m, 3H, ArH), 2.70−2.64 (m, 2H, CCH2C), 2.35−2.29 (m, 5H,
CCH2P, CH3). 31P{1H} NMR (162 MHz, CDCl3): −16.00.
N,N′-Diisopropyl-1,1-diphenylphosphanecarboximidamide
(11a).7c 11a was prepared from 10a (45 μL, 0.5 mmol) and 8 (87 μL,
0.5 mmol) as a colorless oil in 88% yield (0.137 g). H NMR (400
1
MHz, C6D6): δ 7.49−7.44 (m, 4H, ArH), 7.07−7.02 (m, 6H, ArH),
4.47−4.40 (m, 1H, CH), 4.36−4.30 (m, 1H, CH), 3.67−3.65 (d, 1H,
NH J = 6.50 Hz), 1.27−1.25 (d, 6H, J = 6.19 Hz, CH3), 0.97−0.95 (d,
1
6H, J = 6.58 Hz, CH3). P{1H} NMR (162 MHz, CDCl3): −18.70.
N,N′-Dicyclohexyl-1,1-diphenylphosphanecarboximidamide
(11b).7c 11b was prepared from 10b (0.103 g, 0.5 mmol) and 8 (87
μL, 0.5 mmol) as a white solid in 86% yield (0.169 g). 1H NMR (400
MHz, C6D6): δ 7.51−7.47 (m, 4H, ArH), 7.08−7.02 (m, 6H, ArH),
4.14−4.06 (m, 2H, CH), 3.81−3.79 (d, 1H, NH J = 6.13 Hz), 1.90−
1.81 (m, 4H, CH2), 1.72−1.57 (m, 5H, CH2), 1.43−1.21 (m, 11H,
(4-Methoxyphenethyl)diphenylphosphane (9n).4b 9n was pre-
pared from 7n (67 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a
1
colorless oil in 93% yield (0.149 g). H NMR (400 MHz, CDCl3): δ
7.48−7.43 (m, 4H, ArH), 7.35−7.33 (m, 6H, ArH), 7.11−7.08 (d, 2H,
J = 8.86 Hz, ArH), 6.83−6.81 (d, 2H, J = 8.44 Hz, ArH), 3.78 (s, 3H,
OCH3), 2.71−2.65 (m, 2H, CCH2C), 2.37−2.33 (m, 2H, CCH2P).
31P{1H} NMR (162 MHz, CDCl3): −16.16.
1
CH2), 0.99−0.94 (m, 2H, CH2). P{1H} NMR (162 MHz, CDCl3):
−18.31.
(2-([1,1′-Biphenyl]-4-yl)ethyl)diphenylphosphane (9o).20b 9o was
prepared from 7o (0.090 g, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a
N,N′,1,1-Tetraphenylphosphanecarboximidamide (11c).7c 11c
was prepared from 10c (0.097 g, 0.5 mmol) and 8 (87 μL, 0.5
1
1
colorless oil in 80% yield (0.146 g). H NMR (400 MHz, CDCl3): δ
mmol) as a white solid in 82% yield (0.156 g). H NMR (400 MHz,
7.56−7.54 (m, 2H, ArH), 7.50−7.38 (m, 8H, ArH), 7.34−7.28 (m,
7H, ArH), 7.24−7.21 (d, 2H, J = 8.25 Hz, ArH), 2.79−2.73 (m, 2H,
CCH2C), 2.41−2.37 (m, 2H, CCH2P). 31P{1H} NMR (162 MHz,
CDCl3): −15.83.
CDCl3): δ 7.77−7.75 (d, 1H, J = 7.91 Hz, ArH), 7.43−7.39 (m, 4H,
ArH), 7.32−7.30 (m, 1H, ArH), 7.18−7.14 (t, 4H, ArH), 7.11−7.04
1
(m, 8H, ArH), 6.94−6.91 (q, 2H, ArH), 6.52 (s, 1H, NH). P{1H}
NMR (162 MHz, CDCl3): −11.31.
2-(2-(Diphenylphosphanyl)ethyl)pyridine (9p).20b 9s was prepared
from 7s (53 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
in 92% yield (0.134 g). 1H NMR (400 MHz, CDCl3): δ 8.51−8.50 (d,
1H, J = 4.65 Hz, ArH), 7.56−7.51 (m, 1H, ArH), 7.46−7.42 (m, 4H,
ArH), 7.32−7.30 (m, 6H, ArH), 7.09−7.06 (m, 2H, ArH), 2.92−2.85
(m, 2H, CCH2C), 2.51−2.47 (m, 2H, CCH2P). 31P{1H} NMR (162
MHz, CDCl3): −15.43.
N,1,1-Triphenylphosphanecarboxamide (13a).17 13a was pre-
pared from 12a (54 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a white
1
solid in 90% yield (0.137 g). H NMR (400 MHz, CDCl3): δ 7.53−
7.49 (m, 4H, ArH), 7.35−7.34 (m, 6H, ArH), 7.30 (s, 1H, NH), 7.28
(s, 2H, ArH), 7.19−7.15 (t, 2H, ArH), 7.01−6.98 (t, 1H, ArH).
31P{1H} NMR (162 MHz, CDCl3): −0.23.
N-(4-Chlorophenyl)-1,1-diphenylphosphanecarboxamide
(13b).17 13b was prepared from 12b (0.077 g, 0.5 mmol) and 8 (87
μL, 0.5 mmol) as a white solid in 90% yield (0.152 g). 1H NMR (400
MHz, CDCl3): δ 7.51−7.47 (m, 4H, ArH), 7.35−7.32 (m, 7H, ArH,
NH), 7.25−7.23 (d, 2H, J = 8.95 Hz, ArH), 7.13−7.11 (d, 2H, J = 8.76
Hz, ArH). 31P{1H} NMR (162 MHz, CDCl3): 0.14.
4-(2-(Diphenylphosphanyl)ethyl)pyridine (9q).20b 9t was prepared
from 7t (54 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless oil
1
in 87% yield (0.127 g). H NMR (400 MHz, CDCl3): δ 8.46−8.44
(dd, 2H, J = 3.10 Hz, J = 6.40 Hz, ArH), 7.44−7.40 (m, 4H, ArH),
7.35−7.32 (m, 6H, ArH), 7.06−7.08 (d, 2H, J = 5.96 Hz, ArH), 7.09−
7.06 (m, 2H, ArH), 2.72−2.65 (m, 2H, CCH2C), 2.35−2.31 (m, 2H,
CCH2P). 31P{1H} NMR (162 MHz, CDCl3): −15.99.
N-(4-Bromophenyl)-1,1-diphenylphosphanecarboxamide
(13c).17 13c was prepared from 12c (0.099 g, 0.5 mmol) and 8 (87 μL,
Diphenyl(2-phenylpropyl)phosphane (9r).13e 9r was prepared
from 7r (66 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a colorless
oil in 37% yield (0.056 g). 1H NMR (400 MHz, CDCl3): δ 7.36−7.31
(m, 4H, ArH), 7.24−7.22 (m, 5H, ArH), 7.20−7.18 (m, 2H, ArH),
7.13−7.08 (m, 3H, ArH), 2.73−2.66 (m, 1H, CH), 2.40−2.34 (m, 1H,
CH2), 2.25−2.19 (m, 1H, CH2), 1.33(d, 3H, J = 7.2 Hz, CH3).
31P{1H} NMR (162 MHz, CDCl3): −20.05.
1
0.5 mmol) as a white solid in 90% yield (0.178 g). H NMR (400
MHz, CDCl3): δ 7.52−7.47 (m, 4H, ArH), 7.36−7.34 (m, 6H, ArH),
7.32 (brs, 1H, NH), 7.29−7.26 (d, 2H, J = 8.74 Hz, ArH), 7.20−7.18
(d, 2H, J = 8.87 Hz, ArH). 31P{1H} NMR (162 MHz, CDCl3): 0.22.
N-(4-Methoxyphenyl)-1,1-diphenylphosphanecarboxamide
(13d).17 13d was prepared from 12d (65 μL, 0.5 mmol) and 8 (87 μL,
1
0.5 mmol) as a white solid in 83% yield (0.139 g). H NMR (400
(Z)-Diphenyl(styryl)phosphane (9s).20b 9v was prepared from 7v
(55 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a white solid in 40%
yield (0.058 g). 1H NMR (400 MHz, CDCl3): δ 7.51−7.49 (d, 2H, J =
7.80 Hz, ArH), 7.44−7.43 (m, 4H, ArH), 7.35−7.23 (m, 10H, ArH,
CH), 6.47−6.44 (dd, 1H, J = 2.17 Hz, J = 2.35 Hz, PCH). 31P{1H}
NMR (162 MHz, CDCl3): −24.80.
MHz, CDCl3): δ 7.52−7.48 (m, 4H, ArH), 7.33−7.32 (m, 6H, ArH),
7.24 (brs, 1H, NH), 7.23−7.20 (d, 2H, J = 9.32 Hz, ArH), 6.71−6.69
(d, 2H, J = 8.95 Hz, ArH). 31P{1H} NMR (162 MHz, CDCl3): −0.78.
N-(Naphthalen-1-yl)-1,1-diphenylphosphanecarboxamide
(13e).17 13e was prepared from 12e (72 μL, 0.5 mmol) and 8 (87 μL,
1
0.5 mmol) as a white solid in 71% yield (0.126 g). H NMR (400
(3-Methylbut-2-en-1-yl)diphenylphosphine Sulfide (9t).20a 9w
was prepared from 7w (50 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol)
as a colorless oil in 85% yield (0.122 g). 1H NMR (400 MHz, CDCl3):
δ 7.82−7.76 (m, 4H, J = 7.80 Hz, ArH), 7.50−7.40 (m, 6H, ArH),
5.25−5.19 (m, 1H, CH), 3.29−3.21 (m, 2H, PCH2), 1.66−1.64 (d,
3H, J = 4.78 Hz, CH3), 1.40−1.39 (d, 3H, J = 3.62 Hz, CH3). 31P{1H}
NMR (162 MHz, CDCl3): 41.46.
MHz, CDCl3): δ 8.09−8.07 (d, 1H, J = 7.43 Hz, ArH), 7.75 (brs, 1H,
NH), 7.69−7.67 (d, 1H, J = 8.10 Hz, ArH), 7.60 (brs, 4H, ArH),
7.52−7.50 (d, 1H, J = 8.24 Hz, ArH), 7.37−7.28 (m, 8H, ArH), 7.22−
7.19 (t, 1H, ArH), 6.88−6.86 (d, 1H, J = 8.37 Hz, ArH). 31P{1H}
NMR (162 MHz, CDCl3): −1.08.
1,1-Diphenyl-N-propylphosphanecarboxamide (13f). 13f was
prepared from 12f (19 μL, 0.2 mmol) and 8 (35 μL, 0.2 mmol) in
(Z)-(3,7-Dimethylocta-2,6-dien-1-yl)diphenylphosphine Sulfide
1
(9u).20a 9x was prepared from 7x (86 μL, 0.5 mmol) and 8 (87 μL,
87% yield. H NMR (400 MHz, CDCl3): δ 7.52−7.47 (m, 4H, ArH),
1
7.16−7.14 (m, 7H, ArH, NH), 3.03−2.98 (q, 2H, CH2), 1.18−1.13 (q,
2H CH2), 0.59−0.55 (t, 3H, CH3). 31P{1H} NMR (162 MHz,
CDCl3): −3.88. MS: calcd m/z 272.1204 for C16H19NOP [M + H]+,
found 272.1200.
0.5 mmol) as a colorless oil in 83% yield (0.147 g). H NMR (400
MHz, CDCl3): δ 7.94−7.86 (m, 4H, J = 7.80 Hz, ArH), 7.52−7.47 (m,
6H, ArH), 5.22−5.16 (m, 1H, CCH), 5.05−5.02 (m, 1H, Me2C
CH), 3.36−3.33 (d, 2H, J = 13.92 Hz, CH2), 2.12−2.02 (m, 4H,
CH2), 1.70 (s, 3H, CH3), 1.63−1.55 (m, 6H, CH3). 31P{1H} NMR
(162 MHz, CDCl3): 40.27.
N-Cyclopentyl-1,1-diphenylphosphanecarboxamide (13g). 13g
was prepared from 12g (23 μL, 0.2 mmol) and 8 (35 μL, 0.2
1
Methyl 3-(Diphenylphosphanyl)propanoate (9v).20b 9y was
prepared from 7y (45 μL, 0.5 mmol) and 8 (87 μL, 0.5 mmol) as a
mmol) in 67% yield. H NMR (400 MHz, CDCl3): δ 7.52−7.47 (m,
4H, ArH), 7.16−7.14 (m, 7H, ArH, NH), 3.03−2.98 (q, 2H, CH2),
1.18−1.13 (q, 2H CH2), 0.59−0.55 (t, 3H, CH3). 31P{1H} NMR (162
MHz, CDCl3): −3.88. MS: calcd m/z 298.1361 for C18H21NOP [M +
H]+, found 298.1368.
1
colorless oil in 85% yield (0.037 g). H NMR (400 MHz, CDCl3): δ
7.36−7.31 (m, 4H, ArH), 7.24−7.23 (m, 6H, ArH), 3.54 (s, 3H, CH3),
2.35−2.24 (m, 4H, CH2). 31P{1H} NMR (162 MHz, CDCl3): −0.23.
H
DOI: 10.1021/acs.inorgchem.7b02248
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(3) Pringle, P. G.; Smith, M. B. Platinum(0)-Catalysed Hydro-
phosphination of Acrylonitrile. J. Chem. Soc., Chem. Commun. 1990,
1701−1702.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b02248.
■
S
(4) (a) Basalov, I. V.; Yurova, O. S.; Cherkasov, A. V.; Fukin, G. K.;
Trifonov, A. A. Amido Ln(II) Complexes Coordinated by Bi- and
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Chem. - Eur. J. 2016, 22, 5778−5785.
NMR spectra of complexes 1 and 2 and hydro-
phosphination products (PDF)
Accession Codes
CCDC 1572024 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_
request@ccdc.cam.ac.uk, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: +44 1223 336033.
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AUTHOR INFORMATION
Corresponding Authors
*E-mail for D.Y.: yuandan@suda.edu.cn.
*E-mail for Y.Y.: yaoym@suda.edu.cn.
ORCID
Yingming Yao: 0000-0001-9841-3169
Qi Shen: 0000-0002-0223-3591
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from the National Natural Science
Foundation of China (Grants 21402135) and PAPD is
gratefully acknowledged.
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DOI: 10.1021/acs.inorgchem.7b02248
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