Yttrium anilido hydride: Synthesis, structure, and reactivity

Article abstract of DOI:10.1021/om200651c

The synthesis, structure, and reactivity of the yttrium anilido hydride [LY(NH(DIPP))(μ-H)]₂ (3; L = [MeC(N(DIPP))CHC(Me)(NCH ₂CH₂NMe₂)]^-, DIPP = 2,6- ⁱPr₂C₆H₃)) are reported. The protonolysis reaction of the yttrium dialkyl [LY(CH₂SiMe ₃)₂] (1) with 1 equiv of 2,6-diisopropylaniline gave the yttrium anilido alkyl [LY(NH(DIPP))(CH₂SiMe₃)] (2), and a subsequent σ-bond metathesis reaction of 2 with 1 equiv of PhSiH ₃ offered the yttrium anilido hydride 3. The structure of 3 was characterized by X-ray crystallography, which showed that the complex is a μ-H dimer. 3 shows high reactivity toward a variety of unsaturated substrates, including imine, azobenzene, carbodiimide, isocyanide, ketone, and Mo(CO)₆, giving some structurally intriguing products.

Full text of DOI:10.1021/om200651c

ARTICLE
pubs.acs.org/Organometallics
Yttrium Anilido Hydride: Synthesis, Structure, and Reactivity
Erli Lu, Yaofeng Chen,* 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
b
ABSTRACT: The synthesis, structure, and reactivity of the
yttrium anilido hydride [LY(NH(DIPP))(μ-H)]2 (3; L =
[MeC(N(DIPP))CHC(Me)(NCH2CH2NMe2)]ꢀ, DIPP =
2,6-iPr2C6H3)) are reported. The protonolysis reaction of the
yttrium dialkyl [LY(CH2SiMe3)2] (1) with 1 equiv of 2,6-diiso-
propylaniline gave the yttrium anilido alkyl [LY(NH(DIPP))-
(CH2SiMe3)] (2), and a subsequent σ-bond metathesis reaction
of 2 with 1 equiv of PhSiH3 offered the yttrium anilido hydride
3. The structure of 3 was characterized by X-ray crystallography,
which showed that the complex is a μ-H dimer. 3 shows high
reactivity toward a variety of unsaturated substrates, including
imine, azobenzene, carbodiimide, isocyanide, ketone, and Mo-
(CO)6, giving some structurally intriguing products.
’ INTRODUCTION
6-diisopropylaniline in hexane gave the yttrium anilido alkyl 2 as
a pale yellow solid in 58% isolated yield (Scheme 1). 2 is soluble
in toluene and benzene and slightly soluble in hexane. The
complex was characterized by NMR spectroscopy and elemen-
tal analysis. The reaction of 2 with 1 equiv of PhSiH3 in toluene
gave the desired yttrium anilido hydride 3 as colorless crystals in
69% isolated yield (Scheme 1). 3 is sparingly soluble in toluene
Rare-earth-metal hydrides have attracted intense interest due
to their fascinating structural features and high reactivity.1 The
most widely investigated rare-earth-metal hydrides are those
bearing Cp-type ligands.1aꢀc,2 To further explore the chemistry
of the rare-earth-metal complexes, ancillary ligands other than
Cp and Cp derivatives recently have been introduced.1d,e,3 To
date, most of the reported rare-earth-metal hydrides have been
those supported by one dianionic ancillary ligand (LLnH), two of
the same monoanionic ancillary ligands (L2LnH), or one mono-
anionic ancillary ligand for the dihydrides (LLnH2). Examples of
heteroleptic rare-earth-metal hydrides are very rare.4 Rare-earth-
metal hydrides containing mixed monoanionic ancillary ligands
are of interest, as they have powerful electronic and steric tuning
capability as well as rich structural features. The β-diketiminato
rare-earth-metal complexes have attracted growing attention in
the past decade.5 We have developed β-diketiminato-based
tridentate ligands,5d and these ligands have exhibited excellent
effects on stabilizing a series of rare-earth-metal dialkyl com-
plexes and a scandium terminal imido complex.5d,6 The steric and
electronic features of these ligands give them an advantage in
preventing ligand redistribution reactions. Recently, on the basis
of one of these ligands, we synthesized an yttrium anilido
hydride. The complex shows high reactivity toward a variety of
unsaturated substrates. Herein, we report these results.
1
and benzene and nearly insoluble in hexane. In the H NMR
spectrum of 3, the YꢀH signal is overlapped with the aromatic H
signals.
Single crystals of 3 were grown from a toluene solution and
characterized by X-ray crystallography (Figure 1). 3 is a dimer with a
2-fold screw axis, and two yttrium centers (Y1 and Y1A) are linked
by two bridging hydrido ligands (H5 and H6). The yttrium center
adopts a distorted-octahedral geometry with three nitrogen atoms of
the tridentate ligand [MeC(N(DIPP)CHC(Me)(NCH2CH2-
NMe2)]ꢀ (L; DIPP = 2,6-iPr2C6H3) and a hydrido ligand forming
the equatorial plane and a nitrogen atom of the anilido ligand and
a hydrido ligand occupying the axial positions. The β-diketimi-
nato backbone of L is bonded to the yttrium center at YꢀN
separations of 2.388(3) and 2.353(3) Å; the YꢀN bond of the
pendant arm (2.502(3) Å) is longer than those of the backbone
because the pendant arm acts as a neutral donor while the backbone
is an anionic donor. The CꢀN and CꢀC bond lengths of the
β-diketiminato backbone are between those of typical single and
double bonds, and the N1, C2, C3, C4 and N2 atoms are coplanar,
indicating that there is a delocalized electronic structure. The anilido
ligand is coordinated with a YꢀN bond distance of 2.234(3) Å
’ RESULTS AND DISCUSSION
Synthesis and Crystal Structure of Yttrium Anilido Hydride
(3). The yttrium dialkyl 1 was synthesized as we previously
reported.5d The protonolysis reaction of 1 with 1 equiv of 2,
Received: July 20, 2011
Published: September 26, 2011
r
2011 American Chemical Society
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Scheme 1
Scheme 2
Figure 1. Molecular structure of 3 with ellipsoids set at the 30%
probability level. Isopropyl groups of DIPP, hydrogen atoms (except
hydrides and anilide hydrogen atoms), and toluene molecules in the
lattice have been omitted for clarity. Selected bond lengths (Å) and
angles (deg): Y1 Y1A = 3.748(8), Y1ꢀH5 = 2.16(3), Y1ꢀH6 =
3 3 3
2.13(3), Y1ꢀN1 = 2.388(3), Y1ꢀN2 = 2.353(3), Y1ꢀN3 = 2.502(3),
Y1ꢀN4 = 2.234(3), C1ꢀC2 = 1.518(5), C2ꢀC3 = 1.394(5), C3ꢀC4 =
1.398(6), C4ꢀC5 = 1.519(5), C2ꢀN1 = 1.333(4), C4ꢀN2 = 1.333(5);
H5ꢀY1ꢀH6 = 58.1(19), Y1ꢀH5ꢀY1A = 120.8(3), Y1ꢀH6ꢀY1A =
122.7(3), H5ꢀY1ꢀN4 = 142.4(12), H6ꢀY1ꢀN4 = 87.3(13),
Y1ꢀN4ꢀC33 = 157.0(2), N1ꢀC2ꢀC3 = 125.0(3), C2ꢀC3ꢀC4 =
130.9(3), C3ꢀC4ꢀN2 = 125.4(3).
Reactivity of 3 toward Unsaturated Substrates. The reac-
tion of 3 with a substrate containing a CdN bond was initially
studied. 1H NMR spectral monitoring of the reaction of 3 with 2
equiv of N-benzylidene-2,6-dimethylaniline in C6D6 showed that
3 was almost completely converted into the new complex 4 at
room temperature in 8 h. A subsequent scaled-up reaction in
toluene provided 4 as pale yellow crystals in 64% isolated yield. 4
was characterized by NMR spectroscopy and elemental analysis,
which revealed that the complex is an yttrium amido anilide
and a YꢀNꢀC angle of 157.0(2)°. The distances from Y1 to H5
and H6 of the hydrido ligands are 2.16(3) and 2.13(3) Å,
respectively, falling in the range of 2.00ꢀ2.30 Å observed for
YꢀH bonds in other reported dimeric yttrium μ-hydrido com-
plexes.1b,d The Y1ꢀH5ꢀY1A, Y1ꢀH6ꢀY1A, and H5ꢀY1ꢀH6
angles are 120.8(3), 122.7(3), and 58.1(19)°, respectively, and
1
(Scheme 2). The H NMR spectrum of the complex in C6D6
the Y1, H5, H6, and Y1A atoms are coplanar. The Y Y distance
3 3 3
(3.748(8) Å) is longer than those in the complexes [Y(MeC5H4)2-
(thf)(μ-H)]2 (3.66(1) Å),7 [Y{(Me3Si)2NC(NiPr)2}2(μ-H)]2
(3.6825(5) Å),8 and [Me2Si{NC(Ph)N(2,6-iPr2-C6H3)}2Y-
(μ-H)]2 (3.4661(5) Å)3e and close to that in the complex [Y(η5:η1-
C5Me4CH2SiMe2NCMe3)(thf)(μ-H)]2 (3.7085(8) Å).9
features two doublets at 4.67 and 4.58 ppm for two diastereotopic
hydrogen atoms of ꢀNCH2Arꢀ in the amido ligand, and each
doublet has an integration value of 1 and a 2JHꢀH coupling con-
stant of 13.6 Hz. Therefore, the reaction of 3 with N-benzylidene-
2,6-dimethylaniline selectively gave the addition reaction product,
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Figure 2. Molecular structure of 4 with ellipsoids set at the 30%
probability level. Isopropyl groups of DIPP and hydrogen atoms
(except methylene hydrogen atoms on C34 and anilide hydrogen atom)
have been omitted for clarity. Selected bond lengths (Å) and angles
(deg): YꢀN1 = 2.362(2), YꢀN2 = 2.360(2), YꢀN3 = 2.529(2), Yꢀ
N4 = 2.257(2), YꢀN5 = 2.213(2), N5ꢀC34 = 1.473(3), C1ꢀC2 =
1.514(3), C2ꢀC3 = 1.405(3), C3ꢀC4 = 1.407(3), C4ꢀC5 = 1.505(3),
N1ꢀC2 = 1.338(3), N2ꢀC4 = 1.322(3); N4ꢀYꢀN5 = 116.6(1),
YꢀN5ꢀC34 = 114.9(2), YꢀN5ꢀC41 = 132.2(2), N1ꢀC2ꢀC3 =
124.6(2), C2ꢀC3ꢀC4 = 128.5(2), C3ꢀC4ꢀN2 = 122.8(2).
Figure 3. Molecular structure of 5 with ellipsoids set at the 30%
probability level. Isopropyl groups of DIPP and hydrogen atoms
(except hydrazide hydrogen atom and anilide hydrogen atom) have
been omitted for clarity. Selected bond lengths (Å) and angles (deg):
YꢀN1 = 2.353(2), YꢀN2 = 2.375(2), YꢀN3 = 2.493(2), YꢀN4 =
2.228(2), YꢀN5 = 2.245(2), YꢀN6 = 2.517(2), N5ꢀN6 = 1.441(2),
C1ꢀC2 = 1.516(3), C2ꢀC3 = 1.398(3), C3ꢀC4 = 1.403(3), C4ꢀC5 =
1.518(3), C2ꢀN1 = 1.329(2), C4ꢀN2 = 1.329(3); N5ꢀN6ꢀY =
62.30(8), N6ꢀN5ꢀY = 83.08(9), N5ꢀYꢀN6 = 34.62(5), N4ꢀYꢀN5 =
113.1(1), N4ꢀYꢀN6 = 88.7(1), N1ꢀC2ꢀC3 = 123.8(2), C2ꢀC3ꢀC4 =
128.9(2), C3ꢀC4ꢀN2 = 124.8(2).
and deprotonation at the ortho H of the substrate’s phenyl ring
was not observed.10 4 is soluble in toluene and benzene and
sparingly soluble in hexane. Single crystals of 4 were grown from
a hexane solution and characterized by X-ray crystallography
(Figure 2). 4 is a monomer, in which the yttrium center is five-
coordinate. The geometry of the yttrium center can be described
as a distorted square pyramid with a nitrogen atom of the amido
ligand taking the apical position. The tridentate ligand (L)
coordinates to the yttrium center via N1, N2, and N3 atoms
with YꢀN bond lengths of 2.362(2), 2.360(2), and 2.529(2) Å,
respectively. The yttrium center sits above the N1ꢀC2ꢀC3ꢀ
C4ꢀN2 plane of L with a much longer C3N2 planeꢀY distance
(1.34 Å) in comparison to that in 3 (0.56 Å). However, the
distances from the yttrium center to the C2, C3, and C4 atoms are
longer than 3.20 Å, indicating that the β-diketiminato backbone
of L still acts as a two-σ-electron donor. In 4, the YꢀNamido bond
length is 2.213(2) Å, the YꢀNanilido bond length is 2.257(2) Å,
and the NanilidoꢀYꢀNamido angle is 116.6(1)°. The N5ꢀC34
bond length, 1.473(3) Å, is consistent with a single bond.
The reaction of 3 with azobenzene, which has an NdN bond,
in toluene at room temperature gave the yttrium anilido hydra-
zide 5 as an off-white crystalline solid in 74% isolated yield
(Scheme 2). 5 is sparingly soluble in toluene and benzene and
nearly insoluble in hexane. The complex was characterized by
NMR spectroscopy, elemental analysis, and X-ray crystallogra-
phy. Although there are many examples of the reactions of rare-
earth-metal complexes with azobenzene, most are about the
reduction of azobenzene by divalent rare-earth-metal complexes.11
Reports on the reactions of rare-earth-metal hydrides with
azobenzene are very scarce; the only precedent is that of
[(C5Me5)2Sm(μ-H)]2 with azobenzene, giving the samarium hydra-
zide [(C5Me5)2Sm(PhNNHPh)(thf)].12 X-ray crystallography
showed that 5 is a monomer with a six-coordinate yttrium center,
and the hydrazido ligand [PhNHNPh]ꢀ serves as a bidentate
ligand (Figure 3). The N5ꢀN6 distance of the hydrazido ligand,
1.441(2) Å, is similar to that in [(C5Me5)2Sm(PhNNHPh)(thf)]
Figure 4. Molecular structure of 6 with ellipsoids set at the 30%
probability level. Isopropyl groups of DIPP, hydrogen atoms (except
amidinate hydrogen atoms and anilide hydrogen atoms), and the hexane
molecules in the lattice have been omitted for clarity. Selected bond
lengths (Å) and angles (deg): YꢀN1 = 2.371(3), YꢀN2 = 2.372(3),
YꢀN3 = 2.511(3), YꢀN4 = 2.254(3), YꢀN5 = 2.369(3), YꢀN6 =
2.428(3), N5ꢀC34 = 1.331(5), C34ꢀN6 = 1.309(5), C1ꢀC2 =
1.502(5), C2ꢀC3 = 1.405(5), C3ꢀC4 = 1.408(5), C4ꢀC5 =
1.510(5), C2ꢀN1 = 1.334(4), C4ꢀN2 = 1.339(5); N5ꢀC34ꢀN6 =
119.4(3), C34ꢀN5ꢀY = 92.6(2), C34ꢀN6ꢀY = 90.5(2), N5ꢀYꢀN6
= 56.7(1), N4ꢀYꢀN5 = 96.9(1), N4ꢀYꢀN6 = 150.0(1), N1ꢀC2ꢀC3
= 125.6(3), C2ꢀC3ꢀC4 = 132.6(4), C3ꢀC4ꢀN2 = 125.6(3).
(1.443(7) Å),12 falling within the single-bond range. The YꢀN5
bond is significantly shorter than the YꢀN6 bond, 2.245(2) Å vs
2.517(2) Å, indicating different donating properties between N5
and N6 atoms: the former acts as an anionic donor, while the
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7 exists as a monomer, while the reactions of [(C5H4R)2Ln(μ-H)-
(THF)]2 (R = H, Me; Ln = Y, Er) with tert-butyl isocyanide gave
the η2-N-tert-butylformimidoyl-bridged dimers [(C5H4R)Ln-
1
(μ,η2-HCdNCMe3)]2.14 In the H NMR spectrum of 7, the
signal for the formimidoyl hydrogen appears at 10.89 ppm as a
doublet with a JYꢀH coupling constant of 1.8 Hz. X-ray crystal-
lography showed that the formimidoyl ligand coordinates to the
yttrium center through carbon and nitrogen atoms with YꢀC34
and YꢀN5 bond lengths of 2.374(5) and 2.326(4) Å, respectively,
and the N5ꢀC34 (1.258(7) Å) bond reveals sp2-carbonꢀnitrogen
double-bond character (Figure 5).15 It is noteworthy that the Yꢀ
C34 bond in 7 is significantly shorter than those in the [(C5H5)Y-
(μ,η2-HCdNCMe3)]2 dimer (2.545(5) and 2.561(5) Å).14a 1
H
NMR spectral monitoring of the reaction of 3 with 2 equiv of
benzonitrile in C6D6 showed that 3 was almost completely
converted into a new complex in 40 min at room temperature,
and the complex that formed slowly decomposed into a complicated
mixture. A subsequent scaled-up reaction in toluene provided an
orange oil. Efforts to obtain pure product by recrystallization of
the orange oil have been unsuccessful so far.
To investigate the reactivity of 3 toward substrates containing
a CdO double bond, benzophenone was chosen as the substrate.
The reaction of 3 with 2 equiv of benzophenone in toluene at
room temperature gave the yttrium alkyloxo anilide 8 as a pale
yellow crystalline solid in 92% isolated yield (Scheme 2). 8 was
characterized by NMR spectroscopy and elemental analysis. The
1H NMR spectrum of 8 shows a characteristic singlet around 5.00
ppm for the methine proton of the alkyloxo ligand [OCHPh2]ꢀ,
which results from the addition of the YꢀH bond of 3 to the
CdO double bond of benzophenone.16 The anilide proton of
the [NH(DIPP)]ꢀ ligand displays a broad peak at 4.68 ppm. The
reaction of 3 with CO2 (1.0 atm) at room temperature was also
studied. 1H NMR spectral monitoring showed that the reaction
gave a complicated mixture, and no precipitate formed as the
reaction proceeded.
Figure 5. Molecular structure of 7 with ellipsoids set at the 30%
probability level. Isopropyl groups of DIPP and hydrogen atoms
(except formimidoyl hydrogen atom and anilide hydrogen atom) have
been omitted for clarity. Selected bond lengths (Å) and angles (deg):
YꢀN1 = 2.365(4), YꢀN2 = 2.373(4), YꢀN3 = 2.510(4), YꢀN4 =
2.240(4), YꢀN5 = 2.326(4), YꢀC34 = 2.374(5), C34ꢀN5 = 1.258(7),
C1ꢀC2 = 1.519(7), C2ꢀC3 = 1.410(7), C3ꢀC4 = 1.387(7), C4ꢀC5 =
1.506(7), C2ꢀN1 = 1.328(6), C4ꢀN2 = 1.333(7); N5ꢀC34ꢀY =
72.4(3), C34ꢀN5ꢀY = 76.6(3), N5ꢀYꢀC34 = 31.0(2), N4ꢀYꢀN5 =
93.0(2), N4ꢀYꢀC34 = 119.5(2), N1ꢀC2ꢀC3 = 124.9(5), C2ꢀC3ꢀ
C4 = 129.4(5), C3ꢀC4ꢀN2 = 125.8(4).
latter is a neutral donor. The H6 atom bound to the N6 atom was
located from the Fourier map, and no interaction between the H6
atom and the yttrium center was observed.
3 has both hydrido and anilido ligands, and the addition of a
rare-earth-metalꢀnitrogen bond to the NdCdN bond of the
carbodiimide is known.13 Therefore, the reaction of 3 with 4
equiv of N,N0-diisopropylcarbodiimide was carried out. Monitor-
ing of the reaction in C6D6 by 1H NMR spectroscopy revealed
that 3 was almost completely converted into the yttrium amidi-
nato anilide 6 along with 2 equiv of unreacted N,N0-diisopro-
pylcarbodiimide at room temperature in 5 min. No further
transformation was observed, even when the reaction time was
extended to 24 h. The reaction was scaled up in toluene, and 6
was isolated as a pale yellow solid in 84% yield (Scheme 2). The
complex is soluble in toluene and benzene and nearly insoluble in
hexane. In the 1H NMR spectrum of 6, the ꢀNCHNꢀ signal of
the amidinato ligand appears as a doublet at 8.03 ppm with a
unique JYꢀH coupling constant of 3.0 Hz. The X-ray diffraction
analysis reveals that 6 is a monomer with a six-coordinate yttrium
center (Figure 4). The amidinato ligand coordinates to the
yttrium center through two nitrogen atoms with YꢀN bond
lengths of 2.369(3) and 2.428(3) Å, respectively. The amidinato
ligand displays a delocalized electronic framework. For example,
the N5ꢀC34 (1.331(5) Å) and C34ꢀN6 (1.309(5) Å) bonds
are intermediate between those of typical single and double
bonds, and the N5, N6, C34, C35, and C38 atoms are coplanar.
Reactions of 3 with substrates containing other carbonꢀnitro-
gen unsaturated bonds were also studied. The reaction of 3 with 2
Reduction of coordinated carbon monoxide in transition-
metal carbonyls by metal hydrides has attracted intense interest
and has been extensively studied.17ꢀ19 The reaction of rare-
earth-metal hydrides with transition-metal carbonyls, in contrast,
has been far less studied. To the best of our knowledge,
there have been only two reports: one of [Cp*2ScH(thf)] with
[Cp2W(CO)] or [CpCo(CO)2]20 and the other of [{Cp0Y-
(μ-H)2}4(thf)] (Cp0 =η5-C5Me4SiMe3) with[Cp*M(CO)2(NO)]
(M = Mo, W), [Cp*Re(CO)3], or [Cp*M(CO)2] (M = Rh, Ir).21
The reaction of 3 with 2 equiv of Mo(CO)6 in C6D6 was
monitored by 1H NMR spectroscopy, showing that 3 was almost
completely converted into the new complex 9 at room tempera-
ture in 20 min. A subsequent scaled-up reaction in toluene
provided 9 as pale yellow crystals in 80% isolated yield. 9 was
characterized by NMR spectroscopy, elemental analysis, and
X-ray crystallography, confirming that 9 is a yttrium molybde-
num oxycarbene (Scheme 2). The complex is soluble in toluene
and benzene and nearly insoluble in hexane. The oxycarbene
ligand [HCO]ꢀ of the complex shows a singlet at 13.13 ppm in the
2
1H NMR spectrum and a doublet at 358.1 ppm with a JYꢀC
1
equiv of tert-butyl isocyanide in C6D6 was monitored by H
coupling constant of 20.6 Hz in the 13C NMR spectrum.
9 is stable at room temperature in the solid state but slowly
decomposed into a complicated mixture in a C6D6 solution. In 9,
the yttrium center and molybdenum center are bridged by a
μ-oxycarbene ligand, which coordinates to the yttrium center
through an oxygen atom with a YꢀO bond length of 2.172(4) Å
and to the molybdenum center through a carbon atom with a
NMR spectroscopy. 3 was completely converted into the new
complex 7 in 15 min at room temperature. A subsequent scaled-
up reaction in toluene provided 7 as a yellow crystalline solid in
96% isolated yield. 7 was characterized by NMR spectroscopy,
elemental analysis, and X-ray crystallography, confirming that
7 is an yttrium η2-N-tert-butylformimidoyl anilide (Scheme 2).
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Scheme 3
isocyanide, and benzophenone gave the yttrium amido anilide 4,
yttrium anilido hydrazide 5, yttrium amidinato anilide 6, yttrium
η2-N-tert-butylformimidoyl anilide 7, and yttrium alkyloxo ani-
lide 8, respectively. The addition of the YꢀH bond of 3 to one
coordinated carbon monoxide of Mo(CO)6 provided the hetero-
bimetallic yttrium molybdenum oxycarbene 9, where the oxy-
carbene ligand coordinates to the yttrium center through an
oxygen atom and to the molybdenum center through a carbon
atom. During the reactions of 3 with the studied unsaturated
substrates, the YꢀNanilide bond of the complex remained intact.
Further studies will strive to prepare rare-earth-metal phosphido,
arylthio, and aryloxo hydrides, which are based on the mono-
anionic tridentate nitrogen ligand L.
Figure 6. Molecular structure of 9 with ellipsoids set at the 30%
probability level. Isopropyl groups of DIPP and hydrogen atoms
(except oxycarbene hydrogen atom and anilide hydrogen atom) have
been omitted for clarity. Selected bond lengths (Å) and angles (deg):
YꢀO1 = 2.172(4), MoꢀC34 = 2.136(6), C34ꢀO1 = 1.248(7), Yꢀ
N1 = 2.279(4), YꢀN2 = 2.330(4), YꢀN3 = 2.446(5), YꢀN4 =
2.186(4), MoꢀC35 = 2.008(9), MoꢀC36 = 2.038(7), MoꢀC37 =
2.046(11), MoꢀC38 = 1.995(9), MoꢀC39 = 1.999(8), C1ꢀC2 =
1.509(8), C2ꢀC3 = 1.388(8), C3ꢀC4 = 1.405(9), C4ꢀC5 = 1.490(8),
N1ꢀC2 = 1.333(6), N2ꢀC4 = 1.323(7); YꢀO1ꢀC34 = 152.7(4),
O1ꢀC34ꢀMo = 131.5(5), N4ꢀYꢀO1 = 99.0(2), C34ꢀMoꢀC35 =
87.8(2), C34ꢀMoꢀC36 = 174.8(3), C34ꢀMoꢀC37 = 90.0(3), C34ꢀ
MoꢀC38 = 81.6(3), C34ꢀMoꢀC39 = 87.7(3), N1ꢀC2ꢀC3 =
123.4(5), C2ꢀC3ꢀC4 = 128.8(5), C3ꢀC4ꢀN2 = 124.0(5).
’ EXPERIMENTAL SECTION
General Procedures. All operations were carried out under an
atmosphere of argon using standard Schlenk techniques or in a nitrogen-
filled glovebox. Toluene, hexane, and C6D6 were dried over Na/K alloy,
distilled under vacuum, and stored in the glovebox. 2,6-Diisopropylani-
line, phenylsilane, N-benzylidene-2,6-dimethylaniline, N,N0-diisopropyl-
carbodiimide, and tert-butyl isocyanide were dried over activated 4 Å
molecular sieves, distilled under vacuum, degassed three times by
freezeꢀthawꢀvacuum, and stored in the glovebox. Molybdenum
hexacarbonyl, azobenzene, and benzophenone were purchased from
Aldrich and used without further purification. The yttrium dialkyl 1 was
synthesized as we previously reported.5d 1H and 13C spectra were
recorded on a Varian Mercury 300 MHz spectrometer and a Varian
400 MHz spectrometer at 300 or 400 MHz and at 75 or 100 MHz,
respectively. 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. Elemental analysis was performed by the
Analytical Laboratory of the Shanghai Institute of Organic Chemistry.
[LY(NH(2,6-iPr2-C6H3))(CH2SiMe3)] (2). A solution of 2,6-diiso-
propylaniline (254 mg, 1.43 mmol; in 1 mL of hexane) was added to 1
(848 mg, 1.43 mmol) in 5 mL of hexane at room temperature. After the
mixture stood at room temperature for 30 min, all volatiles were
removed under vacuum. The residue was washed with cold hexane
(1 mL ꢁ 3) and dried under vacuum to afford 2 as a pale yellow solid
MoꢀC bond length of 2.136(6) Å (Figure 6). The YꢀO bond is
slightly longer than those reported for the yttrium phenoxide
derivatives (2.02ꢀ2.15 Å)22 and is shorter than YꢀO bonds in the
yttrium ketone complexes [Cp*2Y(Cl)(OdCPh2)] (2.312(2) Å)23
and [L02Y(OCHPh2)(OdCPh2)] (L0 is a salicylaldiminato ligand)
(2.444(2) Å).22f The MoꢀC bond is close to that in [L00(CO)3Mo0d
C(OMe)Ph] (2.136(4) Å) (L00 is a bidentate phosphite ligand)24
and shorter than MoꢀCcarbene bonds in Mo(0) N-heterocyclic
carbene complexes (2.23ꢀ2.33 Å).25 The CꢀO bond of the
μ-oxycarbene ligand, 1.248(7) Å, is close to that in the scandium cobalt
oxycarbene [Cp*2ScꢀO(H3C)CdCo(CO)Cp] (1.268(4) Å)20
and significantly shorter than that in an oligonuclear yttrium
molybdenum oxycarbene (1.423(10) Å).21 This CꢀO bond is
much shorter than the typical C(sp2)ꢀO single bond (1.35 Å)26
and close to a typical C(sp2)dO double bond (1.21 Å) and that
in the molybdenum formyl complex Cp*Mo(CO)2(PMe3)CHO
(1.212(7) Å).27 The MoꢀC34ꢀO1 and YꢀO1ꢀC34 angles are
131.5(5) and 152.7(4)°, respectively, and the Mo, C34, O1, and Y
atoms are coplanar. On the basis of these structural features, 9 is
best described as two resonance forms, A and B (Scheme 3). The
MoꢀY separation (5.26 Å) is rather long, indicating that there is
no metalꢀmetal interaction. The MoꢀC bonds for the carbonyl
ligands range from 1.995(9) to 2.046(11) Å.
1
(568 mg, 58% yield). H NMR (400 MHz, C6D6, 25 °C): δ (ppm)
7.15ꢀ7.11 (m, 5H, ArH), 6.84 (t, 3JHꢀH = 7.6 Hz, 1H, ArH), 4.91 (s, 1H,
MeC(N)CH), 4.45 (s, br, 1H, YNHAr), 3.30 (sept, 3JHꢀH = 6.8 Hz, 1H,
ArCHMe2), 3.23 (sept, 3JHꢀH = 6.8 Hz, 1H, ArCHMe2), 2.84ꢀ2.79 (m,
4H, ArCHMe2 and NCH2), 2.37 (m, 1H, NCH2), 2.11 (s, 3H, NCH3),
1.90 (m, 1H, NCH2), 1.83 (s, 3H, NCH3), 1.70 (s, 3H, H3CC(N)), 1.63
3
(s, 3H, H3CC(N)), 1.41 (d, JHꢀH = 6.8 Hz, 3H, ArCHMe2), 1.38
(d, 3JHꢀH = 6.8 Hz, 6H, ArCHMe2), 1.32 (d, 3JHꢀH = 6.4 Hz, 6H, Ar
3
3
In summary, the yttrium anilido hydride 3 was synthesized by
using a β-diketiminato-based tridentate ligand (L = [MeC(N-
(DIPP))CHC(Me)(NCH2CH2NMe2)]ꢀ, DIPPd2,6-iPr2C6H3))
as an ancillary ligand. X-ray crystallography showed that 3 is a
dimer with two yttrium centers linked by two bridging hydrido
ligands. The addition of the YꢀH bond of 3 across CdN, NdN,
NdCdN, NC, and CdO bonds of N-benzylidene-2,6-dimethyl-
aniline, azobenzene, N,N0-diisopropylcarbodiimide, tert-butyl
CHMe2), 1.26 (d, JHꢀH = 6.8 Hz, 3H, ArCHMe2), 1.14 (d, JHꢀH
=
7.2 Hz, 3H, ArCHMe2), 1.08 (d, 3JHꢀH = 6.8 Hz, 3H, ArCHMe2), 0.20
(s, 9H, YCH2SiMe3), ꢀ0.70 (dd, 2JHꢀH = 11.2 Hz, 2JYꢀH = 3.6 Hz, 1H,
2
2
YCH2SiMe3), ꢀ0.78 (dd, JHꢀH = 11.2 Hz, JYꢀH = 3.6 Hz, 1H,
YCH2SiMe3). 13C NMR (100 MHz, C6D6, 25 °C): δ (ppm) 166.9,
166.4 (imine C), 152.0, 144.4, 143.3, 143.2, 133.1, 126.2, 124.6, 124.4,
123.0, 115.3 (ArC), 98.5 (MeC(N)CH), 58.1, 47.5, 45.6, 44.5 (NMe2
1
and NCH2), 34.0 (d, JYꢀC = 45.5 Hz, YCH2SiMe3), 30.1, 29.0, 28.0,
5437
dx.doi.org/10.1021/om200651c |Organometallics 2011, 30, 5433–5441

Organometallics
ARTICLE
25.1, 25.0, 24.9, 24.6, 24.5, 24.4, 24.3, 24.2, 23.3 (AriPr and MeC), 4.3
(CH2SiMe3). Anal. Calcd for C37H63N4SiY: C, 65.26; H, 9.33; N, 8.23.
Found: C, 65.14; H, 9.12; N, 8.43.
ArCHMe2), 3.02 (m, 1H, NCH2), 2.90ꢀ2.68 (m, 2H, ArCHMe2 and
NCH2), 2.36 (s, 3H, NMe2), 1.99ꢀ1.84 (br m, 1H, NCH2 or ArCH-
Me2), 1.78 (s, 3H, NMe2), 1.77 (s, 3H, MeC), 1.78ꢀ1.72 (br m, 1H,
NCH2), 1.69 (s, 3H, MeC), 1.60ꢀ1.42 (br m, 3H, ArCHMe2),
[LY(NH(2,6-iPr2-C6H3))(μ-H)]2 (3). A solution of PhSiH3 (79 mg,
0.731 mmol; in 1 mL of toluene) was added to 2 (500 mg, 0.734 mmol)
in 2 mL of toluene at ꢀ35 °C. After the mixture stood at ꢀ35 °C for 18 h,
the reaction solution was concentrated to approximately 0.5 mL and
cooled to ꢀ35 °C to afford 3 as colorless crystals (300 mg, 69% yield).
1H NMR (400 MHz, C6D6, 25 °C): δ (ppm) 7.24 (d, 3JHꢀH = 7.6 Hz,
1H, ArH), 7.17 (m, 1H, ArH), 7.08ꢀ6.99 (m, 4H, ArH and YH), 6.88 (t,
3JHꢀH = 7.6 Hz, 1H, ArH), 5.11 (br s, 1H, YNHAr), 4.79 (s, 1H,
MeC(N)CH), 3.47ꢀ3.36 (m, 2H, ArCHMe2), 3.26 (sept, 3JHꢀH = 6.8
Hz, 1H, ArCHMe2), 3.16 (sept, 3JHꢀH = 6.8 Hz, 1H, ArCHMe2), 3.03
(m, 1H, NCH2), 2.91 (m, 1H, NCH2), 2.08 (s, 3H, NMe2), 1.88 (s, 3H,
NMe2), 1.76 (s, 3H, MeC), 1.72 (m, 1H, NCH2), 1.61 (s, 3H, MeC), 1.54
3
1.40ꢀ1.20 (br m, 3H, ArCHMe2), 1.22 (d, JHꢀH = 6.9 Hz, 3H,
3
ArCHMe2), 1.14 (d, JHꢀH = 6.9 Hz, 3H, ArCHMe2), 1.15ꢀ0.90 (br
m, 6H, ArCHMe2), 0.90 (d, 3JHꢀH = 6.6 Hz, 3H, ArCHMe2), 0.68 (d,
3JHꢀH = 6.9 Hz, 3H, ArCHMe2). 13C NMR (100 MHz, C6D6, 25 °C): δ
(ppm) 167.9, 166.4 (imine C), 154.8, 152.0, 151.9, 148.9, 145.3, 142.7,
129.5, 125.6, 125.0, 124.0, 123.0, 122.4, 115.7, 114.8, 114.2 (ArC), 98.6
(MeC(N)CH), 57.9, 48.2, 48.1, 43.9 (NCH2 and NMe2), 32.0, 29.6,
27.6, 27.4, 26.7, 25.5, 25.4, 25.1, 24.8, 24.7, 24.5, 24.3, 23.9, 22.2 (AriPr
and MeC). Anal. Calcd for C45H63N6Y: C, 69.57; H, 8.17; N, 10.82.
Found: C, 69.58; H, 8.29; N, 10.75.
[LY(NH(2,6-iPr2-C6H3))(η2(N,N0)-iPrNCHNiPr)] (6). N,N0-Di-
isopropylcarbodiimide (34 mg, 0.269 mmol) was added to 3 (80 mg,
0.067 mmol) in 1 mL of toluene at room temperature. After the mixture
stood at room temperature for 30 min, the volatiles were removed under
vacuum to give a yellow oil. The yellow oil was added to 0.5 mL of
hexane, and 6 precipitated from the solution as a pale yellow crystalline
solid (86 mg, 84% yield). 1H NMR (300 MHz, C6D6, 25 °C): δ (ppm)
3
(d, JHꢀH = 6.8 Hz, 3H, ArCHMe2), 1.53 (m, 1H, NCH2), 1.49 (d,
3
3JHꢀH = 6.4 Hz, 3H, ArCHMe2), 1.39 (d, JHꢀH = 6.8 Hz, 3H,
3
3
ArCHMe2), 1.31 (d, JHꢀH = 6.4 Hz, 3H, ArCHMe2), 1.20 (d, JHꢀH
= 6.8 Hz, 3H, ArCHMe2), 1.16 (d, 3JHꢀH = 6.4 Hz, 3H, ArCHMe2), 1.06
3
3
(d, JHꢀH = 6.4 Hz, 3H, ArCHMe2), 0.87 (d, JHꢀH = 6.0 Hz, 3H,
ArCHMe2). 13C NMR (100 MHz, C6D6, 25 °C): δ (ppm) 167.1, 165.9
(imine C), 152.2, 146.1, 145.9, 144.3, 135.0, 132.2, 125.9, 125.4, 124.5,
123.4, 122.7, 114.9 (ArC), 98.3 (MeC(N)CH), 57.8, 48.3, 47.8, 46.9
(NCH2 and NMe2), 30.3, 28.3, 28.0, 27.4, 27.2, 27.0, 26.0, 25.7, 25.4,
24.7, 24.4, 24.2, 23.7, 23.5 (AriPr and MeC). Anal. Calcd for C66H106N8Y2:
C, 66.65; H, 8.98; N, 9.42. Found: C, 66.55; H, 8.90; N, 9.57.
3
3
8.03 (d, JYꢀH = 3.0 Hz, 1H, NCHN), 7.22 (d, JHꢀH = 7.5 Hz, 2H,
ArH), 7.13ꢀ7.09 (m, 3H, ArH), 6.86 (t, 3JHꢀH = 7.8 Hz, 1H, ArH), 4.71
(s, 1H, MeC(N)CH), 4.29 (br s, 1H, YNHAr), 3.50 (sept, 3JHꢀH = 6.3
Hz, 1H, CHMe2), 3.45ꢀ3.25 (m, 4H, NCH2 and CHMe2), 3.24ꢀ2.95
(m, 4H, NCH2 and CHMe2), 2.21 (br s, 3H, NMe2), 2.00 (br s, 3H,
NMe2), 1.76 (s, 3H, MeC), 1.63 (m, 1H, NCH2), 1.60 (s, 3H, MeC), 1.47
(d, 3JHꢀH = 6.9 Hz, 6H, CHMe2), 1.37 (d, 3JHꢀH = 6.6 Hz, CHMe2),
[LY(NH(2,6-iPr2-C6H3))(N(CH2Ph)(2,6-Me2-C6H3))] (4). A
solution of N-benzylidene-2,6-dimethylaniline (35 mg, 0.167 mmol; in
1 mL of toluene) was added to 3 (100 mg, 0.084 mmol) in 2 mL of
toluene at room temperature. After the mixture stood at room tempera-
ture for 12 h, the volatiles were removed under vacuum to give a yellow
oil. The yellow oil was extracted with 2 mL of hexane. After standing at
room temperature for several minutes, 4 precipitated from the hexane
solution as pale yellow crystals (87 mg, 64% yield). 1H NMR (400 MHz,
C6D6, 25 °C): δ (ppm) 7.10 (d, 3JHꢀH = 7.2 Hz, 2H, ArH), 7.08ꢀ6.98
(m, 8H, ArH), 6.88ꢀ6.85 (m, 3H, ArH), 6.80 (t, 3JHꢀH = 7.8 Hz, 1H,
ArH), 4.97 (s, 1H, MeC(N)CH), 4.67 (d, 2JHꢀH = 13.6 Hz, 1H, one H of
PhCH2N AB system), 4.58 (d, 2JHꢀH = 13.6 Hz, 1H, one H of PhCH2N
AB system), 4.32 (br s, 1H, YꢀNHAr), 3.61 (sept, 3JHꢀH = 6.8 Hz, 1H,
ArCHMe2), 3.14 (sept, 3JHꢀH = 7.2 Hz, 1H, ArCHMe2), 3.00 (m, 1H,
NCH2), 2.85ꢀ2.78 (m, 3H, two H of ArCHMe2 and 1H of NCH2), 2.61
(m, 1H, NCH2), 2.29 (s, 6H, NMe2), 1.86 (br s, 3H, ArMe), 1.79 (br s,
3H, ArMe), 1.70 (m, 1H, NCH2), 1.67 (s, 3H, MeC), 1.65 (s, 3H, MeC), 1.47
(d, 3JHꢀH = 6.8 Hz, 3H, ArCHMe2), 1.27ꢀ1.22 (m, 12H, ArCHMe2),
1.10 (d, 3JHꢀH = 6.8 Hz, 9H, ArCHMe2). 13C NMR (100 MHz, C6D6,
25 °C): δ (ppm) 167.0, 166.2 (imine C), 152.4, 151.8, 151.7, 146.8, 143.2,
143.1, 134.3, 134.1, 129.2, 128.9, 127.6, 126.2, 126.1, 124.9, 124.4, 123.1,
121.4, 115.5 (ArC), 99.8 (MeC(N)CH), 58.3, 53.8, 47.2, 45.6, 43.7 (NCH2,
NMe2, and NCH2Ph), 29.7, 29.4, 27.7, 25.8, 25.5, 25.1, 24.9, 24.8, 24.7,
24.3, 23.1, 20.8 (AriPr, MeC, and ArMe). Anal. Calcd for C48H68N5Y: C,
71.71; H, 8.52; N, 8.71. Found: C, 72.11; H, 8.80; N, 8.91.
3
1.30ꢀ1.25 (m, 4H, CH2 of hexane), 1.21 (d, JHꢀH = 7.2 Hz, 3H,
CHMe2), 1.16 (d, 3JHꢀH = 6.6 Hz, 3H, CHMe2), 1.13 (d, 3JHꢀH = 6.9
Hz, 3H, CHMe2), 1.10 (d, 3JHꢀH = 6.9 Hz, 3H, CHMe2), 1.07 (d, 3JHꢀH
= 6.3 Hz, 6H, CHMe2), 0.89 (t, 3JHꢀH = 6.6 Hz, 3H, CH3 of hexane),
0.83 (br, 6H, CHMe2). 13C NMR (75 MHz, C6D6, 25 °C): δ (ppm)
169.7 (d, 2JYꢀC = 2.6 Hz, NCHN), 166.9, 166.2 (imine C), 153.0, 152.9,
145.1, 144.6, 143.5, 133.6, 125.8, 125.3, 123.5, 123.3, 114.4 (ArC), 97.0
(MeC(N)CH), 58.0, 52.9, 48.9, 46.0 (NCH2 and NMe2), 31.9, 29.1,
27.6, 27.4, 26.1, 25.5, 25.3, 25.2, 25.0, 24.9, 23.9, 23.0 (iPr, MeC and CH2
of hexane), 14.3 (CH3 of hexane). Anal. Calcd for C40H67N6Y 0.5
3
C6H14: C, 67.60; H, 9.76; N, 11.00. Found: C, 68.18; H, 9.44; N, 10.88.
[LY(NH(2,6-iPr2-C6H3))(η2(N,C)-(H)CNtBu)] (7). A solution of 3
(100 mg, 0.084 mmol in 2 mL of toluene) was added to tert-butyl
isocyanide (14.0 mg, 0.168 mmol) in 0.5 mL of toluene at room
temperature. After the mixture stood at room temperature for 10 min,
the volatiles were removed under vacuum to give 7 as a pale yellow
crystalline solid (110 mg, 96% yield). 1H NMR (300 MHz, C6D6,
2
t
25 °C): δ (ppm) 10.89 (d, JYꢀH = 2.1 Hz, 1H, BuNCH), 7.20 (d,
3JHꢀH = 7.2 Hz, 2H, ArH), 7.12ꢀ6.98 (m, 3H, ArH), 6.83 (t, 3JHꢀH
=
7.2 Hz, 1H, ArH), 4.95 (br s, 1H, YNHAr), 4.86 (s, 1H, MeC(N)CH),
3.43 (sept, 3JHꢀH = 6.9 Hz, 2H, ArCHMe2), 3.05ꢀ2.87 (m, 5H, NCH2
and ArCHMe2), 1.80 (s, 3H, NMe2), 1.78 (s, 3H, NMe2), 1.75 (s, 3H,
MeC), 1.62 (s, 3H, MeC), 1.43 (d, 3JHꢀH = 6.9 Hz, 6H, ArCHMe2), 1.38
3
3
[LY(NH(2,6-iPr2-C6H3))(η2(N,N0)-PhNHNPh)] (5). A solution
of azobenzene (31 mg, 0.170 mmol in 1 mL of toluene) was added to 3
(100 mg, 0.084 mmol) in 2 mL of toluene at room temperature. After the
mixture stood at room temperature for 3.5 days, the volatiles were
removed under vacuum to give an off-white solid with green oil. The
crude product was washed with hexane (1 mL ꢁ 4) and dried under
vacuum to afford 5 as an off-white crystalline solid (98 mg, 74% yield).
1H NMR (300 MHz, C6D6, 25 °C): δ (ppm) 7.27 (d, 3JHꢀH = 7.5 Hz,
1H, ArH), 7.14ꢀ7.03 (m, 8H, ArH), 6.86ꢀ6.77 (m, 4H, ArH), 6.63 (t,
3JHꢀH = 6.9 Hz, 1H, ArH), 6.56ꢀ6.53 (br d, 3JHꢀH = 7.2 Hz, 2H, ArH),
4.89 (s, 1H, MeC(N)CH), 4.11 (br s, 1H, YNHAr or PhNNH(Ph)),
3.97 (br s, 1H, YNHAr or PhNNH(Ph)), 3.43 (sept, 3JHꢀH = 6.9 Hz,
1H, ArCHMe2), 3.31 (m, 1H, NCH2), 3.17 (sept, 3JHꢀH = 6.3 Hz, 1H,
(d, JHꢀH = 7.2 Hz, 3H, ArCHMe2), 1.36 (d, JHꢀH = 6.9 Hz, 6H,
ArCHMe2), 1.22 (d, 3JHꢀH = 6.9 Hz, 3H, ArCHMe2), 1.13 (d, 3JHꢀH
=
6.9 Hz, 3H, ArCHMe2), 1.08 (d, 3JHꢀH = 6.9 Hz, 3H, ArCHMe2), 1.00
(s, 9H, tBuNCH). 13C NMR (100 MHz, C6D6, 25 °C): δ (ppm) 245.2
1
t
(d, JYꢀC = 24.9 Hz, BuNCH), 167.1, 165.6 (imine C), 153.0, 152.9,
144.6, 144.1, 143.3, 133.0, 125.6, 124.3, 124.1, 123.1, 123.0, 114.0 (ArC),
98.1 (MeC(N)CH), 59.6, 58.3, 48.1, 47.6, 44.3 (NCH2, NMe2, and
CMe3), 29.9, 29.6, 28.6, 27.7, 25.4, 25.3, 25.2, 24.7, 24.5, 24.3, 23.6, 23.4
(AriPr, MeC, and CMe3). Anal. Calcd for C38H62N5Y: C, 67.33; H, 9.22;
N, 10.33. Found: C, 67.68; H, 9.28; N, 10.32.
[LY(NH(2,6-iPr2-C6H3))(OCHPh2)] (8). The title compound was
prepared by the procedure described for 7, but with 3 (80 mg, 0.067
mmol) and benzophenone (24.5 mg, 0.134 mmol), and the reaction
5438
dx.doi.org/10.1021/om200651c |Organometallics 2011, 30, 5433–5441

Organometallics
ARTICLE
Table 1. Crystallographic Data and Refinement Details for 3ꢀ7 and 9
3 2(toluene)
4
5
6 0.5(hexane)
7
9
3
3
formula
C
80H122N8Y2
1373.68
colorless
monoclinic
C2/c
C48H68N5Y
803.98
C45H63N6Y
776.92
C43H74N6Y
763.99
C38H62N5Y
677.84
C39H53MoN4O6Y
858.70
fw
color
yellow
colorless
monoclinic
P21/n
pale yellow
triclinic
P1
pale yellow
monoclinic
P21/c
orange
cryst syst
monoclinic
P21/n
monoclinic
P21/n
space group
a, Å
21.552(4)
18.772(4)
19.399(4)
90.00
13.580(1)
15.711(1)
21.773(2)
90.00
11.094(7)
19.042(1)
20.950(1)
90.00
11.955(1)
12.368(1)
14.907(1)
86.963(1)
81.089(1)
78.696(2)
2134.8(3)
2
12.916(3)
14.940(3)
20.858(5)
90.00
14.276(4)
20.640(5)
14.382(4)
90.00
b, Å
c, Å
α, deg
β, deg
92.502(2)
90.00
107.742(1)
90.00
103.220(1)
90.00
107.507(3)
90.00
94.245(4)
90.00
γ, deg
V, Å3
7841(3)
4
4424.5(6)
4
4308.3(4)
4
3838.8(1)
4
4225.9(2)
4
Z
Dcalcd, mg/mm3
1.164
1.207
1.198
1.189
1.173
1.350
F(000)
2944
1720
1656
826
1456
1776
θ range, deg
no. of rflns collected
no. of unique rflns
no. of obsd rflns
no. of params
final R, Rw (I > 2σ(I))
goodness of fit on F2
ΔFmax, min, e Åꢀ3
1.44ꢀ26.00
28 055
1.58ꢀ27.00
31 721
1.46ꢀ26.00
32 275
1.38ꢀ27.00
15 311
1.65ꢀ26.00
19 726
1.73ꢀ27.00
28 884
7661
9638
8440
9145
7527
9174
5692
7284
7415
7492
5013
5830
412
501
489
468
428
470
0.0579, 0.1465
1.081
0.0389, 0.0997
1.090
0.0282, 0.0776
1.017
0.0490, 0.1470
1.064
0.0714, 0.1798
1.040
0.0687, 0.1686
1.011
0.927, ꢀ1.039
0.559, ꢀ0.621
0.754, ꢀ0.467
0.751, ꢀ0.669
1.725, ꢀ1.351
1.555, ꢀ0.831
3
3
time was 30 min. 8 was obtained as a pale yellow crystalline solid (95.2
mg, 92% yield). 1H NMR (300 MHz, C6D6, 25 °C): δ (ppm) 7.40ꢀ7.37
(m, 4H, ArH), 7.32ꢀ7.06 (m, 11H, ArH), 6.89 (t, 3JHꢀH = 7.8 Hz, 1H,
ArH), 5.21 (s, 1H, OCHPh2 or MeC(N)CH), 4.96 (s, 1H, OCHPh2 or
MeC(N)CH), 4.68 (br s, 1H, YNHAr), 3.42 (sept, 3JHꢀH = 6.6 Hz, 1H,
ArCHMe2), 3.10ꢀ2.78 (m, 5H, ArCHMe2 and NCH2), 2.33 (m, 1H,
ArCHMe2 or NCH2), 2.17 (m, 1H, ArCHMe2 or NCH2), 2.13 (s, 3H,
NMe2), 2.01 (s, 3H, NMe2), 1.77 (s, 3H, MeC), 1.68 (s, 3H, MeC), 1.47
(d, JHꢀH = 6.4 Hz, 3H, ArCHMe2), 0.95 (d, JHꢀH = 6.8 Hz, 3H,
ArCHMe2). 13C NMR (100 MHz, C6D6, 25 °C): δ (ppm) 358.1 (d,
2JYꢀC = 20.6 Hz, MoC(H)OY), 216.8, 208.5 (Mo(CO)5), 168.1, 166.6,
151.0, 150.9, 143.4, 142.2, 140.2, 133.2, 126.9, 124.9, 124.7, 123.0, 116.5
(ArC), 99.5 (MeC(N)CH), 57.6, 47.3, 46.5, 42.2 (NCH2 and NMe2),
31.3, 28.8, 28.0, 25.1, 24.5, 24.1, 23.8, 23.7, 23.5, 23.3 (AriPr and MeC).
Anal. Calcd for C39H53MoN4O6Y: C, 54.55; H, 6.22; N, 6.52. Found: C,
54.11; H, 6.27; N, 6.42.
3
3
(d, JHꢀH = 6.9 Hz, 6H, ArCHMe2), 1.38 (d, JHꢀH = 6.6 Hz, 6H,
X-ray Crystallography. Suitable single crystals of 3ꢀ7 and 9 were
mounted under a nitrogen atmosphere on a glass fiber, and data
collection was performed at 173(2) K (for 3) or 133(2) K (for 4ꢀ7
and 9) 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,
except for the hydrogen atoms of YꢀH in 3 and the anilide hydrogen
atom H4 and the hydrazide hydrogen atom H6 in 5, which were located
from the Fourier map. All calculations were carried out using the
SHELXL-97 program. The software used is given in ref 28. Crystal-
lographic data and refinement details for 3ꢀ7 and 9 are given in Table 1.
3
ArCHMe2), 1.18ꢀ1.10 (m, 9H, ArCHMe2), 1.05 (d, JHꢀH = 6.3 Hz,
3H, ArCHMe2). 13C NMR (75 MHz, C6D6, 25 °C): δ (ppm) 167.4,
166.1 (imine C), 152.2, 152.1, 150.0, 149.9, 144.5, 143.2, 142.6, 132.8,
128.2, 127.0, 126.6, 126.2, 126.1, 125.6, 124.6, 124.2, 122.8, 114.7 (ArC),
98.5 (MeC(N)CH), 81.3 (d, 2JYꢀC = 4.4 Hz, OCHPh2), 57.9, 47.6, 44.8,
44.7 (NCH2 and NMe2), 30.2, 28.4, 28.3, 25.5, 24.6, 24.3, 24.2, 24.1,
24.0, 23.7, 23.5 (AriPr and MeC). Anal. Calcd for C46H63N4OY: C,
71.11; H, 8.17; N, 7.21. Found: C, 70.70; H, 8.16; N, 7.02.
[LY(NH(2,6-iPr2-C6H3))(μ-OCH)Mo(CO)5] (9). A solution of 3
(100 mg, 0.084 mmol; in 2 mL of toluene) was added to molybdenum
hexacarbonyl (44 mg, 0.167 mmol) in 1 mL of toluene at ꢀ35 °C. After
the addition, the solution was warmed to room temperature. After the
mixture stood at room temperature for 30 min, the volatiles were
removed under vacuum to give a yellow viscous oil. The yellow oil
was added to 1 mL of hexane, and 9 precipitated from the solution as a
yellow crystalline solid (115 mg, 80% yield). 1H NMR (400 MHz, C6D6,
25 °C): δ (ppm) 13.13 (s, 1H, CHO), 7.20ꢀ7.18 (m, 3H, ArH), 7.07
(dd, 3JHꢀH = 7.6 Hz, 4JHꢀH = 1.2 Hz, 1H, ArH), 7.02 (dd, 3JHꢀH = 7.2
Hz, 4JHꢀH = 1.6 Hz, 1H, ArH), 6.90 (t, 3JHꢀH = 7.6 Hz, 1H, ArH), 5.07
(br s, 1H, YNHAr), 4.93 (s, 1H, MeC(N)CH), 3.04ꢀ2.88 (m, 4H,
NCH2 and ArCHMe2), 2.73 (m, 1H, NCH2), 2.65ꢀ2.57 (m, 2H,
ArCHMe2), 2.43 (s, 3H, NMe2), 2.06 (s, 3H, NMe2), 1.83 (m, 1H,
NCH2), 1.68 (s, 3H, MeC), 1.51 (s, 3H, MeC), 1.43 (d, 3JHꢀH = 6.4 Hz,
6H, ArCHMe2), 1.33 (d, 3JHꢀH = 6.8 Hz, 6H, ArCHMe2), 0.99 (d, 3JHꢀH
= 7.2 Hz, 3H, ArCHMe2), 0.98 (d, 3JHꢀH = 6.8 Hz, 3H, ArCHMe2), 0.96
’ ASSOCIATED CONTENT
S
Supporting Information. CIF files giving X-ray crystal-
b
lographic data for 3ꢀ7 and 9. This material is available free of
charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: yaofchen@mail.sioc.ac.cn. Fax: (+86)21-64166128.
5439
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Organometallics
ARTICLE
’ ACKNOWLEDGMENT
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This work was supported by the National Natural Science
Foundation of China (Grant Nos. 20872164 and 20821002), the
State Key Basic Research & Development Program (Grant No.
2011CB808705), Shanghai Municipal Committee of Science and
Technology (10DJ1400104), and the Chinese Academy of Sciences.
(12) Evans, W. J.; Kociok-K€ohn, G.; Leong, V. S.; Ziller, J. W. Inorg.
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