C-P or C-H bond cleavage of phosphine oxides mediated by an yttrium hydride

Article abstract of DOI:10.1021/om300369f

Reactions of the yttrium anilido hydride [LY(NH(DIPP))(μ-H)]₂ (1; L = [MeC(N(DIPP))CHC(Me)(NCH₂CH₂NMe ₂)]^-, DIPP = 2,6-ⁱPr₂C ₆H₃)) with three phosphine oxid

Full text of DOI:10.1021/om300369f

Article
pubs.acs.org/Organometallics
C−P or C−H Bond Cleavage of Phosphine Oxides Mediated by an
Yttrium Hydride
Erli Lu, Yaofeng Chen,* Jiliang Zhou, and Xuebing Leng
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345
Lingling Road, Shanghai 200032, People’s Republic of China
S
* Supporting Information
ABSTRACT: Reactions of the yttrium anilido hydride
[LY(NH(DIPP))(μ-H)]2 (1; L = [MeC(N(DIPP))CHC-
(Me)(NCH2CH2NMe2)]−, DIPP = 2,6-iPr2C6H3)) with
three phosphine oxides and two phosphine sulfides are
reported. The reaction of 1 with Ph3PO gives C−P bond
cleavage and an yttrium anilido phosphinoyl complex, while
those with R2MePO (R = Me, Ph) result in C−H bond
cleavage and two yttrium anilido alkyl complexes. 1 also reacted with R3PS (R = Me, Ph), which demonstrated P−S bond
cleavage via hydride-based reduction and gave an yttrium anilido sulfide.
ond cleavage and formation is the focus of synthetic
constant of 5.2 Hz. A subsequent scaled-up reaction in toluene
provided 2 as a white crystalline solid in 56% yield. Complex 2
was characterized by NMR spectroscopy (1H, 13C, and 31P-
{1H}), elemental analysis, and single-crystal X-ray diffraction,
confirming that 2 is an yttrium anilido phosphinoyl complex, as
shown in Scheme 1. Thus, in the reaction of 1 with Ph3PO,
B
chemistry. There are numerous examples concerning C−
H,1 C−O,2 C−N,3 and C−S4 bond cleavage mediated by
transition-metal complexes. In comparison, the examples of
transition-metal-mediated C−P bond cleavage are fewer, and
most of these involve the C−P bond cleavage of PR3 (R = aryl
or alkyl group).5
The phosphine oxides (R3PO) are an important class of
organophosphorus compounds.6 Due to the stability of
phosphine oxides, they are commonly used as neutral dative
ligands in transition-metal complexes.7 There are a few
examples of phosphine oxides acting as oxygen-transfer
reagents with P−O bond cleavage.8 The C−P bond cleavage
of phosphine oxides mediated by transition-metal complexes
has been rarely observed, and most of the examples involve the
oxidative addition of low-valent palladium to the C−P bond.9
Herein we present reactions of an yttrium anilido hydride with
three phosphine oxides and two phosphine sulfides. Depending
on the substrates, C−P, C−H, or P−S bond cleavage was
observed.
Scheme 1
one CPh−P bond of Ph3PO is cleaved and a [O−PPh2]−
anion is formed. To the best of our knowledge, 2 is the first
rare-earth-metal diorganophosphinoyl complex. It is note-
worthy that the reaction of the rare-earth-metal hydride
[Cp*2Sm(μ-H)]2 with Ph3PO results in o-CPh−H bond
cleavage and the cyclometalated product [Cp*2SmC6H4P(O)-
Ph2].11 It is also noteworthy that Hill and co-workers recently
reported that the reaction of {Ca[N(SiMe3)2]2(OPPh3)2} or
{Ca[CH(SiMe3)2]2(OPPh3)2} with PhSiH3 occurred to give
CPh−P bond cleavage, in which the calcium hydride was
proposed as the reaction intermediate.12 As a consequence of
the formation of 2, C6H6 was observed when we carried out the
reaction of 1 with 2 equiv of Ph3PO in d8-toluene (Figure
S13, Supporting Information).
RESULTS AND DISCUSSION
■
Reaction of 1 with Ph3PO. When the yttrium anilido
hydride [LY(NH(DIPP))(μ-H)]2 (1; L = [MeC(N(DIPP))-
CHC(Me)(NCH2CH2NMe2)]−, DIPP = 2,6-iPr2C6H3)10 was
mixed with 2 equiv of triphenylphosphine oxide (Ph3PO) in
C6D6 at room temperature, the reaction solution turned from
pale yellow to brown immediately and to pale yellow again
within 2 min. 1H NMR spectroscopic monitoring of the
reaction showed that 1 was mostly converted into the new
complex 2 in 1 h with concomitant formation of a minor
amount of other intractable contaminants. 31P{1H} NMR
spectroscopy revealed the disappearance of Ph3PO and the
formation of a new phosphorus compound which displays a
Received: May 2, 2012
Published: June 5, 2012
2
doublet at 91.7 ppm with a characteristic JY−P coupling
© 2012 American Chemical Society
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The molecular structure of 2 is shown in Figure 1. The most
interesting structural feature of 2 is the monoanionic
group of MeR2PO (R = Me, Ph) is cleaved instead of the C−
P bond.
Scheme 2
The molecular structures of 3 and 4 are shown in Figure 2. In
3 and 4, the monoanionic ligand [R2P(O)CH2]− coordinates to
the yttrium center in a κ2(C,O) manner. The Y−O bonds in 3
and 4 (2.307(2) and 2.323(3) Å) are much longer than that in
2 (2.121(3) Å), because the O atom acts as a neutral donor in 3
and 4 but as an anionic donor in 2. The Y−C bond lengths in 3
and 4 are 2.585(2) and 2.604(4) Å, respectively. The P−O
bond (1.548(2) Å for 3, 1.538(3) Å for 4) is shorter than the
P−O single bond in 2 (1.576(3) Å) and longer than the PO
double bond in Ph3PO (1.499(2) Å).14
Figure 1. Molecular structure of 2 with ellipsoids set at the 30%
probability level. Isopropyl groups at the DIPP substituents and
hydrogen atoms (except the anilide hydrogen atom) have been
omitted for clarity. Selected bond lengths (Å) and angles (deg): Y−O
= 2.121(3), Y−N1 = 2.328(3), Y−N2 = 2.339(3), Y−N3 = 2.489(3),
Y−N4 = 2.210(3), P−O = 1.576(3), P−C34 = 1.836(4), P−C40 =
1.837(4), C1−C2 = 1.511(5), C2−C3 = 1.390(5), C3−C4 =
1.398(6), C4−C5 = 1.510(5), C2−N1 = 1.338(5), C4−N2 =
1.325(5); Y−O−P = 151.1(2), O−P−C34 = 104.5(2), O−P−C40 =
103.1(2), C34−P−C40 = 96.2(2), Y−N4−C22 = 152.5(3).
Reactions of 1 with R3PS (R = Ph, Me). The reaction of
1 with triphenylphosphine sulfide (Ph3PS) was also studied.
The reaction of 1 with 2 equiv of Ph3PS in C6D6 led to
nearly complete conversion of 1 into the new complex 5 at
room temperature in 15 min with concomitant formation of
PPh3 (−5.3 ppm in the 31P{1H} NMR spectrum) and H2 (4.47
phosphinoyl ligand. The phosphinoyl ligand coordinates to
the yttrium center with a Y−O bond of 2.121(3) Å, which falls
in the range 2.02−2.15 Å observed for Y−O single bonds in
yttrium alkyloxy/aryloxy complexes.13 The phosphorus atom of
the phosphinoyl ligand is pyramidal (O−P−C34 = 104.5(2)°,
O−P−C40 = 103.1(2)°, C34−P−C40 = 96.2(2)°; ∑ = 303°)
with a lone electron pair situated at the top of the pyramid. The
distance from the phosphorus atom to the yttrium center, 3.58
Å, is long, indicating that there is no interaction between the
lone electron pair of phosphorus and the empty d orbital of
yttrium. The P−O bond (1.576(3) Å), which is significantly
longer than the PO double bond in Ph3PO (1.499(2)
Å),14 is consistent with a single bond. The P−Cipso bond
lengths (1.836(4) and 1.837(4) Å) are close to those in Ph3P
O (1.798−1.801 Å).14
1
ppm in the H NMR spectrum) and unreacted Ph3PS. No
further transformation was observed when the reaction time
was extended to 12 h. A subsequent scaled-up reaction in
toluene with a reactant molar ratio of 1:1 provided 5 as a pale
yellow crystalline solid in 82% yield. Complex 5 was
characterized by NMR spectroscopy (1H and 13C), elemental
analysis, and single-crystal X-ray diffraction, confirming that 5 is
an yttrium anilido sulfide (Scheme 3).
The foregoing observation revealed that the reaction is a
hydride-based reduction, as shown in Scheme 4,15 and the P−S
bond of Ph3PS was cleaved in this case. The molecular
structure of 5 is shown in Figure 3. In 5, the two yttrium
centers are bridged by a μ-S2− ligand. Y1−S and Y2−S bond
lengths are 2.548(1) and 2.545(1) Å, respectively, which are
obviously shorter than those in the μ3-S2− yttrium(III) complex
[(Cp2Y)2(μ3-S)(thf)]2 (2.63−2.70 Å).16 The Y1−S−Y2 angle
is 165.72(5)°. The reaction of 1 with Me3PS proceeded in a
Reactions of 1 with MeR2PO (R = Me, Ph). To
investigate the influence of the substituents on the phosphorus
atom in the reaction, the reactions of 1 with Me3PO and
1
same way as that with Ph3PS, and H NMR spectroscopic
1
MePh2PO were studied. H NMR spectroscopic monitoring
monitoring of the reaction in C6D6 showed the formation of 5,
PMe3, and H2 (Figure S12, Supporting Information).
In summary, reactions of the yttrium anilido hydride 1 with
three phosphine oxides (Ph3PO, Me3PO, and MePh2P
O) and two phosphine sulfides (Ph3PS and Me3PS) show
diverse reaction patterns. Depending on the substrate, C−P,
C−H, or P−S bond cleavage was observed. It is noteworthy
that the reaction of 1 with Ph3PO gives the first example of a
rare-earth-metal diorganophosphinoyl complex via C−P bond
cleavage.
of the reaction of 1 with 2 equiv of Me3PO or MePh2PO
in C6D6 showed that 1 was almost completely converted into
the new complex 3 or 4 in 15 or 45 min at room temperature,
and the formation of hydrogen gas (H2) was observed (4.47
ppm). In the 31P{1H} NMR spectra, the signal for Me3PO or
MePh2PO disappeared, while a new signal at 53.1 ppm for
the reaction with Me3PO or at 47.7 ppm for the reaction
with Ph2MePO was observed. Subsequent scaled-up
reactions in toluene provided 3 and 4 as white crystalline
solids in 70% and 58% yields, respectively. Complexes 3 and 4
were characterized by NMR spectroscopy (1H, 13C, and
31P{1H}), elemental analysis, and single-crystal X-ray diffrac-
tion, which revealed that 3 and 4 are the yttrium anilido alkyl
complexes (Scheme 2). Therefore, in the reaction of 1 with
Me3PO or MePh2PO, one C−H bond on the methyl
EXPERIMENTAL SECTION
■
General Procedures. All operations were carried out under an
atmosphere of argon using Schlenk techniques or in a nitrogen-filled
glovebox. Toluene, hexane, C6D6, and d8-toluene were dried over Na/
K alloy, distilled under vacuum, and stored in the glovebox. Ph3PO,
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Figure 2. Molecular structures of 3 and 4 with ellipsoids set at the 30% probability level. Isopropyl groups of the DIPP substituents and hydrogen
atoms (except the anilide hydrogen atoms) have been omitted for clarity. Selected bond lengths (Å) and angles (deg) for 3: Y−O = 2.307(2), Y−
C36 = 2.585(2), Y−N1 = 2.405(2), Y−N2 = 2.314(2), Y−N3 = 2.615(2), Y−N4 = 2.242(2), O−P = 1.548 (2), P−C34 = 1.795(3), P−C35 =
1.791(3), P−C36 = 1.721(2), C1−C2 = 1.520(3), C2−C3 = 1.421(3), C3−C4 = 1.409(4), C4−C5 = 1.523(4), C2−N1 = 1.324(3), C4−N2 =
1.322(3); Y−C36−P = 86.5(9), C36−P−O = 106.8(1), P−O−Y = 101.1(8), O−Y−C36 = 64.6(6), C34−P−C35 = 106.0(1). Selected bond lengths
(Å) and angles (deg) for 4: Y−O = 2.323(3), Y−C34 = 2.604(4), Y−N1 = 2.370(4), Y−N2 = 2.363(4), Y−N3 = 2.496(4), Y−N4 = 2.265(4), P−O
= 1.538(3), P−C34 = 1.721(4), P−C35 = 1.817(5), P−C41 = 1.809(4), C1−C2 = 1.507(6), C2−C3 = 1.401(7), C3−C4 = 1.405(7), C4−C5 =
1.509(7), C2−N1 = 1.347(6), C4−N2 = 1.316(6); Y−C34−P = 86.2(2), C34−P−O = 106.9(2), P−O−Y = 101.2(1), O−Y−C34 = 63.9(1), C35−
P−C41 = 106.3(2).
Scheme 3
Scheme 4
Figure 3. Molecular structure of 5 with ellipsoids set at the 30%
probability level. Isopropyl groups of the DIPP substituents, hydrogen
Me3PO, MePh2PO, and Ph3PS were purchased from Alfa-
Aesar and used without further purification. Me3PS was preapred
from the reaction of PMe3 with S. The yttrium anilido hydride 1 was
synthesized as we previously reported.10 1H, 13C, and 31P{1H} NMR
spectra were recorded on a Varian Mercury 300 MHz or a Varian 400
MHz spectrometer. All chemical shifts are reported in δ units with
reference to the residual solvent resonance of the deuterated solvents
for proton and carbon chemical shifts and to external H3PO4 (85%)
for phosphorus chemical shifts. Elemental analysis was performed by
the Analytical Laboratory of Shanghai Institute of Organic Chemistry.
[LY(NH(2,6-iPr2-C6H3)(OPPh2)] (2). Ph3PO (46.8 mg, 0.168
mmol) in 1 mL of toluene was added to 1 (100 mg, 0.084 mmol) in 3
mL of toluene at room temperature. The reaction solution turned
from pale yellow to brown immediately and to pale yellow again within
5 min. After the reaction solution stood at room temperature for 2 h,
the volatiles were removed under vacuum to give a yellow solid. The
solid was extracted with hexane (2 × 2 mL), and the extract was
cooled to −35 °C to afford 2 as a white crystalline solid (117 mg,
0.094 mmol, 56% yield). 1H NMR (400 MHz, C6D6, 25 °C): δ (ppm)
7.60 (m, 2H, ArH), 7.31 (m, 2H, ArH), 7.21−7.17 (m, 4H, ArH),
atoms (except the anilide hydrogen atoms), and solvent molecules in
the lattice have been omitted for clarity. Selected bond lengths (Å) and
angles (deg): Y1−S = 2.548(1), Y2−S = 2.545(1), Y1−N1 = 2.356(3),
Y1−N2 = 2.337(3), Y1−N3 = 2.515(3), Y1−N4 = 2.205(3), Y2−N5
= 2.346(3), Y2−N6 = 2.337(3), Y2−N7 = 2.507(3), Y2−N8 =
2.219(3), C1−C2 = 1.507(5), C2−C3 = 1.399(5), C3−C4 =
1.405(5), C4−C5 = 1.523(5), C2−N1 = 1.333(5), C4−N2 =
1.334(5), C33−C34 = 1.507(5), C34−C35 = 1.396(5), C35−C36 =
1.402(5), C36−C37 = 1.519(5), C34−N5 = 1.339(5), C36−N6 =
1.327(5); Y1−S−Y2 = 165.72(5), Y1−N4−C22 = 151.3(3), Y2−N8−
C54 = 152.1(3).
3
3
MeC), 1.40 (d, JH−H = 7.2 Hz, 6H, ArCHMe2), 1.32 (d, JH−H = 6.4
Hz, 6H, ArCHMe2), 1.26 (d, 3JH−H = 6.8 Hz, 3H, ArCHMe2), 1.23 (d,
3JH−H = 6.8 Hz, 3H, ArCHMe2), 1.10 (d, JH−H = 6.4 Hz, 3H,
3
ArCHMe2), 1.09 (d, JH−H = 6.8 Hz, 3H, ArCHMe2). 13C NMR (100
3
MHz, C6D6, 25 °C): δ (ppm) 167.6, 166.7 (imine C), 151.7 (d, 3JP−C
= 4.4 Hz, Cmeta of P−Ph), 150.8 (d, JP−C = 29.0 Hz, Cipso of P−Ph),
1
150.1 (d, JP−C = 28.8 Hz, Cipso of P−Ph), 150.0, 143.7, 143.3, 142.6,
1
3
7.13−7.00 (m, 7H, ArH), 6.88 (t, JH−H = 7.6 Hz, 1H, ArH), 4.92 (s,
133.1 (ArC), 129.8 (d, JP−C = 23.2 Hz, Cortho of P−Ph), 129.2 (d,
2
1H, MeC(N)CH), 4.87 (br, 1H, Y−NHDIPP), 3.37 (sept, 3JH−H = 6.8
Hz, 1H, ArCHMe2), 3.04−2.86 (m, 4H, ArCHMe2 and NCH2), 2.75
(m, 1H, NCH2), 2.27 (m, 1H, NCH2), 2.13 (s, 3H, NMe2), 2.03 (s,
3H, NMe2), 1.96 (m, 1H, NCH2), 1.68 (s, 3H, MeC), 1.57 (s, 3H,
2JP−C = 23.8 Hz, Cortho of P−Ph), 127.5, 126.3 (ArC), 124.6 (d, 3JP−C
=
3.0 Hz, Cmeta of P−Ph), 122.9, 115.4 (ArC), 99.0 (MeC(N)CH), 58.1,
47.6, 46.0, 43.6 (NCH2 and NMe2), 31.9, 30.4, 28.7, 28.5, 25.2, 24.9,
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24.8, 24.3, 24.2, 24.1, 23.7, 23.6, 23.0 (AriPr and MeC). 31P{1H} NMR
(162 MHz, C6D6, 25 °C): δ (ppm) 91.7 (d, JY−P = 5.2 Hz, Y−
OPPh2). Anal. Calcd for C45H62N4OPY: C, 68.00; H, 7.86; N, 7.05.
Found: C, 68.79; H, 7.94; N, 7.27.
two isomers. The A:B ratio changes from 1:0.2 to 1:0.3 when the
complex’s C6D6 solution temperature is increased from 25 to 80 °C
and goes back to 1:0.2 when the solution temperature is decreased to
25 °C. The NMR spectral data of the major isomer A are presented
here. 1H NMR (400 MHz, C6D6, 25 °C): δ (ppm) 7.19 (d, 3JH−H = 7.6
Hz, 2H, ArH), 7.01 (m, 3H, ArH), 6.85 (t, 3JH−H = 7.6 Hz, 1H, ArH),
4.91 (s, 1H, MeC(N)CH), 4.85 (s, 1H, Y−NHDIPP), 3.64 (sept,
2
[LY(NH(2,6-iPr2-C6H3)(κ2(C,O)-CH2P(O)Me2)] (3). Me3PO
(15.5 mg, 0.168 mmol) in 1 mL of toluene was added to 1 (100
mg, 0.084 mmol) in 2 mL of toluene at −35 °C. Evolution of gas (H2)
was observed immediately. After the reaction solution stood at room
temperature for 1 h, the volatiles were removed under vacuum to give
a pale orange solid. The solid was washed with cold hexane (3 × 0.5
mL) and dried under vacuum to afford 3 as a white crystalline solid
3
3JH−H = 6.8 Hz, 1H, ArCHMe2), 3.17 (sept, JH−H = 6.4 Hz, 1H,
ArCHMe2), 3.07 (m, 1H, NCH2), 2.98−2.88 (m, 4H, NCH2 and
ArCHMe2), 2.08 (s, 3H, NMe2), 1.77 (s, 3H, NMe2), 1.71 (s, 3H,
3
MeC), 1.65 (m, 1H, NCH2), 1.59 (s, 3H, MeC), 1.46 (d, JH−H = 6.8
1
(80.6 mg, 0.117 mmol, 70% yield). Some H, 13C, and 31P NMR
Hz, 6H, ArCHMe2), 1.44 (d, 3JH−H = 6.8 Hz, 6H, ArCHMe2), 1.43 (d,
3
3JH−H = 6.8 Hz, 3H, ArCHMe2), 1.29 (d, JH−H = 6.8 Hz, 3H,
signals of the complex are broad at 25 °C and become sharp at 60 °C.
1H NMR (400 MHz, C6D6, 25 °C): δ (ppm) 7.16−7.13 (m, 5H,
ArCHMe2), 1.18 (d, 3JH−H = 6.8 Hz, 3H, ArCHMe2), 1.13 (d, 3JH−H
=
3
6.8 Hz, 3H, ArCHMe2). 13C NMR (100 MHz, C6D6, 25 °C): δ (ppm)
167.0, 166.4 (imine C), 152.2, 145.8, 144.0, 143.0, 132.9, 129.3, 128.5,
125.6, 125.3, 124.5, 124.0, 122.9, 114.8 (ArC), 99.0 (MeC(N)CH),
56.9, 50.2, 47.8, 43.1 (NCH2 and NMe2), 30.2, 28.1, 28.0, 25.7, 25.3,
24.8, 24.6, 24.3, 24.2, 23.1 (AriPr and MeC). Anal. Calcd for
C66H104N8SY2·C7H8: C, 66.85; H, 8.61; N, 8.54. Found: C, 66.50; H,
8.64; N, 8.57.
ArH), 6.81 (t, JH−H = 7.6 Hz, 1H, ArH), 4.92 (s, 1H, MeC(N)CH),
4.18 (br, 1H, Y−NHDIPP), 3.90 (br, 1H, ArCHMe2 or NCH2), 3.50−
2.95 (br, 5H, ArCHMe2 and NCH2), 2.13 (s, 3H, NMe2), 2.00 (br, 3H,
NMe2), 1.76 (s, 3H, MeC), 1.72 (br, 1H, ArCHMe2 or NCH2), 1.69 (s,
3H, MeC), 1.60−0.80 (m, 30H, ArCHMe2 and PMe2), 0.44 (br, 2H,
YCH2P(O)). 1H NMR (400 MHz, C6D6, 60 °C): δ (ppm) 7.14−7.09
3
(m, 5H, ArH), 6.74 (t, JH−H = 7.2 Hz, 1H, ArH), 4.92 (s, 1H,
MeC(N)CH), 4.23 (br, 1H, Y−NHDIPP), 3.79 (br, 1H, ArCHMe2 or
NCH2), 3.40−3.14 (br, 2H, ArCHMe2 or NCH2), 3.08−2.96 (br, 2H,
ArCHMe2 or NCH2), 2.08 (br, 6H, NMe2), 1.85 (m, 1H, ArCHMe2 or
X-ray Crystallography. Suitable single crystals of 2−5 were
mounted under a nitrogen atmosphere on a glass fiber, and data
collection was performed at 133(2) K on a Bruker APEX2
diffractometer with graphite-monochromated Mo Kα radiation (λ =
0.710 73 Å). The SMART program package was used to determine the
unit cell parameters. The absorption correction was applied using
SADABS. The structures were solved by direct methods and refined
on F2 by full-matrix least-squares techniques with anisotropic thermal
parameters for non-hydrogen atoms. Hydrogen atoms were placed at
calculated positions and were included in the structure calculations. All
calculations were carried out using the SHELXL-97 program. The
software used is given in ref 17. Crystallographic data and refinement
details for 2−5 are given in Table S1 (Supporting Information).
3
NCH2), 1.79 (s, 3H, MeC), 1.69 (s, 3H, MeC), 1.43 (d, JH−H = 6.4
Hz, 3H, ArCHMe2), 1.38−1.14 (br, 15H, ArCHMe2), 1.09 (d, 3JH−H
=
6.8 Hz, 3H, ArCHMe2), 1.04 (br, 3H, ArCHMe2), 0.42 (s, 2H,
YCH2P(O)). 13C NMR (100 MHz, C6D6, 60 °C): δ (ppm) 165.2
(imine C), 152.8, 144.3, 133.6, 133.4, 125.8, 124.8, 123.7, 122.9, 114.4
(ArC), 96.6 (MeC(N)CH), 59.7, 47.4 (NCH2 and NMe2), 28.3 (d,
1JP−C = 23.6 Hz, PMe2), 25.1, 25.0, 24.9, 24.6, 24.4, 24.1, 24.0, 22.3,
20.6, 20.3, 18.7, 18.1 (MeC or AriPr), 15.5 (dd, 1JY−C = 60.8 Hz, 1JP−C
= 17.1 Hz, Y−CH2P). 31P{1H} NMR (162 MHz, C6D6, 25 °C): δ
(ppm) 53.1 (s, Y−CH2P(O)). 31P{1H} NMR (162 MHz, C6D6, 60
2
°C): δ (ppm) 52.9 (d, JY−P = 6.4 Hz, Y−CH2P(O)). Anal. Calcd for
C36H60N4OPY: C, 63.14; H, 8.83; N, 8.18. Found: C, 62.66; H, 9.07;
N, 8.02.
ASSOCIATED CONTENT
* Supporting Information
■
S
[LY(NH(2,6-iPr2-C6H3)(κ2(C,O)-CH2P(O)Ph2)] (4). 4 was obtained
by the procedure described for 3, but with 1 (100 mg, 0.084 mmol)
and MePh2PO (36 mg, 0.168 mmol), as a white crystalline solid
CIF files giving X-ray crystallographic data for 2−5, a table
giving crystallographic data and refinement parameters for 2−5,
and figures giving NMR spectra of 2−5 and 1H NMR spectra of
the reaction of 1 with 1 equiv of Me3PS in C6D6 and the
reaction of 1 with 2 equiv of Ph3PO in d8-toluene. This
material is available free of charge via the Internet at http://
pubs.acs.org.
1
(79.2 mg, 0.098 mmol, 58% yield). H NMR (300 MHz, C6D6, 25
°C): δ (ppm) 7.93 (m, 2H, ArH), 7.74 (m, 2H, ArH), 7.08 (m, 11H,
3
ArH), 6.77 (t, JH−H = 7.2 Hz, 1H, ArH), 4.60 (s, 1H, MeC(N)CH),
3
4.29 (br s, 1H, Y−NHDIPP), 4.03 (sept, JH−H = 7.2 Hz, 1H,
ArCHMe2), 3.28−3.10 (m, 3H, ArCHMe2 and NCH2), 2.89 (m, 1H,
NCH2), 2.30 (s, 3H, NMe2), 2.10 (s, 3H, NMe2), 1.89 (m, 1H,
3
NCH2), 1.62 (s, 3H, MeC), 1.47 (d, JH−H = 6.6 Hz, 3H, ArCHMe2),
AUTHOR INFORMATION
Corresponding Author
*E-mail: yaofchen@mail.sioc.ac.cn. Fax: (+86)21-64166128.
3
■
1.35 (d, JH−H = 6.6 Hz, 3H, ArCHMe2), 1.32 (s, 3H, MeC), 1.30 (d,
3JH−H = 6.9 Hz, 3H, ArCHMe2), 1.16−1.06 (m, 17H, ArCHMe2 and
Y−CH2P). 13C NMR (75 MHz, C6D6, 25 °C): δ (ppm) 164.4, 162.9
3
(imine C), 152.5 (d, JP−C = 3.7 Hz, Cmeta of P−Ph), 152.4, 147.7,
Notes
1
144.1, 141.9 (ArC), 139.4 (d, JP−C = 39.9 Hz, Cipso of P−Ph), 138.1
The authors declare no competing financial interest.
(d, 1JP−C = 43.9 Hz, Cipso of P−Ph), 131.2 (d, 2JP−C = 10.5 Hz, Cortho of
3
2
P−Ph), 130.8 (d, JP−C = 1.8 Hz, Cmeta of P−Ph), 130.7 (d, JP−C
=
ACKNOWLEDGMENTS
10.3 Hz, Cortho of P−Ph), 130.3 (d, JP−C = 1.6 Hz, Cmeta of P−Ph),
125.8, 124.8, 123.4, 122.9, 114.4 (ArC), 96.5 (MeC(N)CH), 59.8,
47.0, 46.3, 43.6 (NCH2 and NMe2), 28.8, 27.9, 25.2, 25.1, 24.8, 24.7,
■
3
This work was supported by the State Key Basic Research &
Development Program (Grant No. 2011CB808705), the
National Natural Science Foundation of China (Grant Nos.
21072209, 21132002, and 21121062), and the Chinese
Academy of Sciences.
24.3, 22.1 (AriPr and MeC), 11.8 (dd, JY−C = 68.0 Hz, JP−C = 16.4
Hz; Y−CH2P). 31P{1H} NMR (121 MHz, C6D6, 25 °C): δ (ppm)
47.7 (d, 2JY−P = 8.4 Hz; Y−CH2P(O)). Anal. Calcd for C46H64N4OPY:
C, 68.30; H, 7.97; N, 6.93. Found: C, 68.46; H, 8.04; N, 6.78.
[(LY(NHDIPP))2(μ-S)] (5). Ph3PS (24.5 mg, 0.084 mmol) in 0.5
mL of toluene was added to 1 (100 mg, 0.084 mmol) in 2 mL of
toluene at −35 °C. Evolution of gas (H2) was observed immediately.
After the reaction solution stood at room temperature for 30 min, the
volatiles were removed under vacuum to give a pale yellow solid. The
solid was recrystallized in a mixture of toluene and hexane to afford 5
as colorless crystals (82.0 mg, 0.0672 mmol, 82% yield). 5 exists as the
two isomers A and B with an A:B ratio of of 1:0.2 at room temperature
in C6D6 solution. Repeated recrystallization did not change the ratio of
1
1
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