Reactivity studies of (Phenylethynyl)germylene LGeC≡CPh (L = HC[C(Me)N-2,6- i Pr2C6H3]2) toward pentafluorophenylcopper(I), -silver(I), and -gold(I) complexes

Article abstract of DOI:10.1021/om300724t

Reactions of (phenylethynyl)germylene LGeC≡CPh (L = HC[C(Me)N-2,6-iPr₂C₆H₃]₂) with 0.25 equiv of (CuC₆F₅)₄, 1 equiv of AgC ₆F₅·MeCN, and 1 equiv of AuC₆F ₅·SC₄H₈, respectively, yielded LGe(C≡CPh)CuC₆F₅ (1), [(LGeC≡CPh) ₂Ag]⁺[Ag(C₆F₅)₂] ^- (2), and LGe(C≡CPh)AuC₆F₅ (3). Complexes 1-3 were characterized by IR and NMR spectroscopy and X-ray crystallography. Compound 1 shows a bonding pattern of the CuC₆F ₅ entity by both the phenylethynyl C≡C linkage and the L ligand backbone of the γ-C atom, while 3 exhibits a bonding mode of the AuC ₆F₅ entity at the germylene center. Compound 2 is an ionic derivative featuring the Ge-Ag donor-acceptor bond formed under redistribution of the AgC₆F₅ entity. Further reactions of 1 with (CuC₆F₅)₄, AgC₆F₅· MeCN, and AuC₆F₅·SC₄H₈ afforded the complexes LGe(C≡CPh)(CuC₆F₅)(MC ₆F₅) (M = Cu (4), Ag (5), Au (6)). Compounds 4-6 were characterized by IR and NMR spectroscopy, and 5 and 6 were further investigated by X-ray crystallography. Compounds 4-6 all show an additional bonding of the respective MC₆F₅ moiety at the germylene center of 1. These studies reveal a multiple donor reactivity of LGeC≡CPh. The slightly different Lewis acidic properties of the congeneric pentafluorophenylcopper(I), -silver(I), and -gold(I) complexes as acceptors are thus disclosed.

Full text of DOI:10.1021/om300724t

Article
pubs.acs.org/Organometallics
Reactivity Studies of (Phenylethynyl)germylene LGeCCPh (L =
HC[C(Me)N-2,6‑iPr2C6H3]2) toward Pentafluorophenylcopper(I),
-silver(I), and -gold(I) Complexes
Na Zhao,† Jinyuan Zhang,† Ying Yang,† Guifang Chen,† Hongping Zhu,*,† and Herbert W. Roesky‡
†State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of
Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, People’s
Republic of China
‡Institut fur Anorganische Chemie, Universitat Gottingen, Tammannstrasse 4, 37077, Gottingen, Germany
̈
̈
̈
̈
S
* Supporting Information
ABSTRACT: Reactions of (phenylethynyl)germylene
LGeCCPh (L = HC[C(Me)N-2,6-iPr2C6H3]2) with 0.25
equiv of (CuC6F5)4, 1 equiv of AgC6F5·MeCN, and 1 equiv of
AuC6F5·SC4H8, respectively, yielded LGe(CCPh)CuC6F5
(1), [(LGeCCPh)2Ag]+[Ag(C6F5)2]− (2), and LGe(C
CPh)AuC6F5 (3). Complexes 1−3 were characterized by IR
and NMR spectroscopy and X-ray crystallography. Compound
1 shows a bonding pattern of the CuC6F5 entity by both the phenylethynyl CC linkage and the L ligand backbone of the γ-C
atom, while 3 exhibits a bonding mode of the AuC6F5 entity at the germylene center. Compound 2 is an ionic derivative featuring
the Ge−Ag donor−acceptor bond formed under redistribution of the AgC6F5 entity. Further reactions of 1 with (CuC6F5)4,
AgC6F5·MeCN, and AuC6F5·SC4H8 afforded the complexes LGe(CCPh)(CuC6F5)(MC6F5) (M = Cu (4), Ag (5), Au (6)).
Compounds 4−6 were characterized by IR and NMR spectroscopy, and 5 and 6 were further investigated by X-ray
crystallography. Compounds 4−6 all show an additional bonding of the respective MC6F5 moiety at the germylene center of 1.
These studies reveal a multiple donor reactivity of LGeCCPh. The slightly different Lewis acidic properties of the congeneric
pentafluorophenylcopper(I), -silver(I), and -gold(I) complexes as acceptors are thus disclosed.
reactivities of such germylene species LGeCCPh toward
INTRODUCTION
■
pentafluorophenylcopper(I), -silver(I), and -gold(I) complexes.
Different types of group 11 metal(I)−germylene complexes
were generated to reveal the interaction of either the
phenylethynyl donor or the germylene site. Herein, we report
on these reactions and isolation and characterization of a series
of new group 11 metal(I)−germylene complexes.
A monoanionic N,N′-chelate ligand (L = HC[C(Me)N-2,6-
iPr2C6H3]2) has been extensively employed for synthesizing the
heteroleptic germylene compound LGeR due to a kinetic
intramolecular donor stabilization.1 The R substituent has been
tuned in a number of compounds with a germylene center.2−4
The germylene center contains a lone pair of electrons capable
of bonding to transition metals.2c,f
Transition-metal−
5−7
−i,
germylene chemistry has attracted special attention due to
addition reactions of small molecules across the M−Ge
bond.2f,h,8−10 The group 10 and 11 metal germylene complexes
have been found to activate small molecules such as H2, CO2,8b
O2,8c,9 and COS.8d Recently, we and others have prepared
complexes of the LGeR type with R = halide, alkyl, aryl,
alkoxide, amide, phosphide, where L is a β-diketiminato,3b,11
guanidinato,2g or pyrrolyaldiminato ligand.12 We also prepared
and structurally characterized complexes [LGeMe(CuC6F5)n]2
(n = 1, 2), LGe[C(SiMe3)N2]AgC6F5, and {LGe[C(SiMe3)-
N2](AgC6F5)2}2 (L = HC[C(Me)N-2,6-iPr2C6H3]2) with a
M−Ge bond.13 The incorporation of the R donor functionality
at the germylene center provides a further bonding site for
different metal fragments. It appears intriguing to see whether
the donor R could collaborate or compete with the adjacent
germylene center. During subsequent investigations by altering
the R on the alkynyl functionality, we found multiple donor
RESULTS AND DISCUSSION
■
The β-Diketiminato ligand-stabilized (phenylethynyl)-
germylene LGeCCPh (L = HC[C(Me)N-2,6-iPr2C6H3]2)
has been reported as one of the products from the addition
reaction of phenylacetylene with the ylide-like germylene L′Ge
(L′ = HC[C(CH2)N-2,6-iPr2C6H3][C(Me)N-2,6-iPr2C6H3])
in a low yield (16%).14 For a preparation perspective, we used a
convenient route to LGeCCPh by a one-pot synthesis
through multiple-step metathesis reactions without isolation of
the intermediate LGeCl. As summarized in Scheme 1, LH
reacted with nBuLi to form LLi, which was directly used for the
reaction with GeCl2·(dioxane) to produce LGeCl. Subse-
quently, LGeCl reacted by chloride−phenylacetylide exchange
Received: July 30, 2012
Published: January 24, 2013
© 2013 American Chemical Society
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Scheme 1. One-Pot Synthesis of LGeCCPh
with PhCCLi to afford LGeCCPh as a yellowish
crystalline solid in high yield (90%).
Using LGeCCPh as the precursor, we first carried out the
reaction with the pentafluorophenylcopper(I) complex. The
reaction of LGeCCPh with 0.25 equiv of (CuC6F5)4
proceeded smoothly in toluene at room temperature, and
compound LGe(CCPh)CuC6F5 (1) was produced (Scheme
2). Compound 1 was isolated as light yellow crystals in a yield
of 71%. It has been fully characterized by IR and NMR (1H,
13C, and 19F) spectroscopy, X-ray crystallography, and
elemental analysis. The structural analysis reveals that the
formation of 1 may involve strong interactions of the CuC6F5
entity with both the phenylethynyl CC linkage and the L
ligand backbone of the γ-CH group. This result is remarkably
different from that of the previously reported copper(I)−
Figure 1. X-ray crystal structure of 1 with iPr of the Ar at L omitted
for clarity. Selected bond lengths (Å) and angles (deg): Ge(1)−N(1)
= 1.994(2), Ge(1)−N(2) = 1.994(2), Ge(1)−C(31) = 2.043(3),
Cu(1)−C(31) = 1.982(3), Cu(1)−C(32) = 2.074(3), Cu(1)−C(3) =
2.233(3), Cu(1)−C(41) = 1.943(3), N(1)−C(2) = 1.324(4), N(2)−
C(4) = 1.320(4), C(1)−C(2) = 1.498(5), C(2)−C(3) = 1.416(5),
C(3)−C(4) = 1.432(5), C(4)−C(5) = 1.502(5), C(31)−C(32) =
1.239(5); N(1)−Ge(1)−N(2) = 91.05(12), N(1)−Ge(1)−C(31) =
90.03(13), N(2)−Ge(1)−C(31) = 90.44(13), Ge(1)−C(31)−C(32)
= 164.2(3), C(31)−C(32)−C(33) = 164.4(3), C(31)−Cu(1)−C(32)
= 35.47(14).
germylene bonding reactions.1 9,13 The H and 13C NMR
spectra display the L ligand backbone of the γ-CH proton
resonance at δ 5.75 ppm and that of the carbon at δ 88.79 ppm.
Both of these chemical shifts are significantly different in
comparison to those of LGeCCPh (δ 5.10, 100.1 ppm)14
and the related Ge−Cu-bound complexes [LGe(Me)CuC6F5]2
(δ 4.76, 98.5 ppm) and [LGe(Me)(CuC6F5)2]2 (δ 4.73, 99.2
ppm).13 The phenylethynyl CC carbon atoms resonate at a
lower field (δ 121.18, 115.58 ppm) in comparison with those of
LGeCCPh (δ 113.0, 103.3 ppm).14 The IR spectrum shows
h,
1
36.7(3)°).19 Correspondingly, the CC bond length
(1.234(4) Å) appears slightly longer than that in LGeC
CPh (1.219(5) Å),14 although the difference is negligible.
These structural data evidence a Cu−η2-CC π-complexation
in agreement with the results from IR and NMR spectroscopy.
The Cu···Cγ‑CH separation is 2.236(3) Å, which is longer than
the Cu−CCC bond distance but distinctly shorter than the
corresponding van der Waals radii (3.10 Å), indicating a strong
Cu···Cγ‑CH interaction. Due to this interaction, the Cγ‑CH atom
the CC absorption band at ν
̃
1957 cm−1, which is red-shifted
by ca. 160 cm−1 relative to that in LGeCCPh (ν
̃
2117 cm−1).
These data indicate a π complexation between the CuC6F5
moiety and the CC linkage. In addition, the 19F NMR
spectrum exhibits resonances at δ −111.38 (o-F), −160.097 (p-
F), and −161.51 ppm (m-F) with an integral intensity ratio of
2:1:2, similar to those typical of strong donor-molecule-
interacting pentafluorophenylcopper(I) complexes.15−18 The
Δδ(19Fm,p) value of δ 1.42 ppm is indicative of a terminally
bound C6F5 group at the Cu center.18
is in a tetrahedral geometry similar to those found in the PPCl
−
2
20
Cγ‑CH bound compound LPCl2 and the bicyclo[2.2.2]octane-
type complex L″Ge (L″ = HC[C(CH2)N-2,6-iPr2C6H3][C-
(Me)N-2,6-iPr2C6H3][C(R)CH], R = H, Ph).14 This
suggests that a Cu−Cγ‑CH covalent bond is formed. However,
we noted that within the C3N2Ge ring in 1 the CCN−Cγ‑CH
bond lengths (1.427(4) and 1.418(4) Å) and the C−N
distances (1.326(4) and 1.319(4) Å) have changed slightly in
The crystal structure of 1 shows a bridging of the
F5C6Cu−η2-CCPh part over the central C3N2Ge ring by
the γ-C and the Ge atom as a result of the strong interactions of
the CuC6F5 entity with the CC linkage and the γ-CH group
(Figure 1). The Cu−CCC bond lengths of 1.982(3) and
2.074(3) Å and the CCC−Cu−CCC angle of 35.47(14)° are
both in the range typical of those found in the copper(I)−η2-
alkynyl complexes (1.935(7)−2.201(5) Å, 35.4(2)−
comparison with those in LGeCCPh (CCN−Cγ‑CH
=
1.390(3) Å, C−N = 1.345(3) Å).14 We also noted that in
LPCl2 a CCN−Cγ‑CH single bond (1.514(5) and 1.532(5) Å)
and a C−N double bond (1.281(5) and 1.284(5) Å) are
formed.20 Furthermore, in the compound (L′′′CpZrCl)2[B-
(C6F5)3]2 (L′′′ = HC[C(Me)NC6H5]2), the central C3N2 part
Scheme 2. Plausible Bond Rearrangement Formation of 1
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of the L′′′ is found to be in a σ,π ligation at the Zr atom due to
steric hindrance. The CCN−Cγ‑CH bond lengths are 1.422(3)
and 1.410(4) Å, and the C−N distances are 1.342(4) and
1.325(4) Å.21 Obviously it can be seen, by focusing on the
structural parameters of the C3N2Ge ring, that the CCN−Cγ‑CH
and C−N bond lengths in 1 are intermediate between those of
conjugated and nonconjugated systems of other comparable
complexes. However, small differences of the related parame-
ters are indicated due to the different coordination environ-
ments. Therefore, we can argue that the formation of 1 might
involve an initial bonding of the CuC6F5 entity at the
phenylethynyl CC linkage followed by a nucleophilic attack
of the CC bond from the C3N2Ge skeleton to the Cu center,
giving zwitterionic 1, which largely resonates to a C3N2Ge
ring···CuC6F5 π-complexation mode (Scheme 2).
Further reactions of LGeCCPh were performed with the
pentafluorophenylsilver(I) and -gold(I) complexes, and as a
result, different types of products were formed. Treatment of
LGeCCPh with 1 equiv of AgC6F5·MeCN in toluene at
room temperature in the absence of light resulted in the
formation of [(LGeCCPh)2Ag]+[Ag(C6F5)2]− (2). The
reaction with 1 equiv of AuC6F5·SC4H8 in toluene at room
temperature produced LGe(CCPh)(AuC6F5) (3) (Scheme
3). Compound 2 was isolated as yellow crystals in 65% yield
heterocyclic germylenes (NHGes) have been discussed to be
relatively weak.1d Therefore, the formation of 2 is mostly
attributed to the Lewis acidity of the AgC6F5 that causes a
strong interaction with the germylene. Compound 2 represents,
to our knowledge, the first example as a result of a
redistribution of the organosilver(I) species under interaction
with the NHGe. The Ge−Ag bond lengths are 2.4731(10) and
2.4732(10) Å and are nearly comparable to those in the
complex (R2ATI)(X)GeAg{HB[3,5-(CF3)2Pz]3} (2.4116(10)−
2.4215(9) Å; R2ATI = N-alkyl-2-(methylamino)troponiminate,
R = nPr, X = Cl;4 R = Me, X = Cl, O3SCF3;6a R = nPr, X =
N36b) and the calculated complex [HC(H)N]2GeAgCl (2.448
Å).26 The small differences might be due to steric hindrance
from the bulky L ligand at the Ge center. The geometry of the
coordinated Ag whether in the cation (176.23(2)°) or in the
anion (179.4(2)°) is almost linearly arranged. In the structure
of 3, the Ge−Au bond length is 2.3683(6) Å (2.3641(7) Å for
another molecule) and can be compared to that in R′(Cl)-
GeAuI (2.346(2) Å, R′ = (2-C5H4N)C(Me3Si)C(Ph)N-
(Me3Si)).2f In the germaaurate compounds Ph3PAuGeCl3
(2.406(1) Å), (Ph3P)3AuGeCl3 (2.536(1) Å),27 (Ph4P)[MeC-
(CH2NSiMe3)3Ge]2Au (2.423(2) Å),28 and LAuGeX[N-
(SiMe3)2]2 (2.4085(3)−2.4169(5) Å; X = Cl, L = PPh3,
PCy3, PEt3; X = F, L = PPh3),29 the Ge−Au distances appear
slightly longer. The Au atom adopts a nearly linear geometry
(Ge(1)−Au(1)−C(41) = 176.64(14)°; 174.30(17)° for
another molecule).
Scheme 3. Formation of 2 and 3
The interaction of the AgC6F5 and AuC6F5 moieties with the
germylene in 2 and 3 is significantly different from that of 1.
This might be due to the different Lewis acidic properties of
CuC6F5, AgC6F5, and AuC6F5, although they contain the same
C6F5 group. Compound 1 still carries an unreacted germylene
donor site. This prompted us to examine further reactions of 1
with (CuC6F5)4, AgC6F5·MeCN, and AuC6F5·SC4H8, respec-
tively. The reactions of 1 with 0.25 equiv of (CuC6F5)4 or 1
equiv of AgC6F5·MeCN or AuC6F5·SC4H8 were accomplished
under conditions similar to those when LGeCCPh was used
as the precursor. The additional F5C6M−germylene donor−
acceptor bound compounds LGe(CCPh)(CuC6F5)(MC6F5)
(M = Cu (4), Ag (5), Au (6)) were generated as expected
(Scheme 4). In comparison, 2 and 3 both have a free
phenylethynyl group. However, no reaction was observed when
2 and 3 were reacted with AgC6F5·MeCN or AuC6F5·SC4H8.
Compounds 5 and 6 were isolated as yellow crystals in 72% and
57% yields, respectively. Compound 4 was produced as a
yellow solid in 43% yield. Compound 4 is almost insoluble in
and 3 as colorless crystals in 71% yield. Both compounds have
been confirmed by IR and NMR (1H, 13C, and 19F)
spectroscopy and X-ray crystallography. The IR spectra display
the CC absorption band at ν
̃
2145 for 2 and 2135 cm−1 for 3.
The 13C NMR spectra record the CC carbon atom
resonances at δ 123.55 and 104.72 ppm for 2 and at δ
104.83 and 101.37 ppm for 3, respectively. These data suggest a
free phenylethynyl CC linkage without any π bonding, which
1
1
organic solvents. Its H and 19F NMR spectral data were only
is different from that in 1. Meanwhile, the combined H and
13C NMR spectra show the L ligand backbone of the γ-CH
proton and the carbon resonances at δ 4.98 and 100.30 ppm for
2 and at δ 4.96 and 100.39 ppm for 3, respectively, which are
close to those of LGeCCPh,14 indicating no further bonding
of the γ-CH group by the AgC6F5 or AuC6F5 fragment.
obtained by an in situ measurement of the NMR tube reaction
in C6D6, and the related 13C NMR data were not available.
Compounds 5 and 6 have been fully characterized by NMR
(1H, 13C, and 19F) and IR spectroscopy and X-ray
crystallography. Due to the limited solubility of 5, its 13C
NMR spectrum did not give clear resonances whether in
aromatic (C6D6) or in chlorinated (CDCl3 or CD2Cl2)
hydrocarbons after a long time of spectral acquisition.
The X-ray structural analysis clearly discloses 2 as an ionic
compound with one Ag+ bound by two LGeCCPh molecules
to form a cation while the other Ag+ coordinates to the two
C6F5 groups constituting the anionic counterpart. In contrast,
compound 3 forms the coordinated F5C6Au−germylene
complex. The crystal structures of 2 and 3 are depicted in
Figures 2 and 3. The structure of 2 can be compared with that
of [Ag(NHC)2]+[AgX2]− (NHC = N-heterocyclic carbene, X =
halide). The latter compound is considered to be formed by
redistribution of the AgX under interaction with the strong
NHC donor.22−25 However, the donor reactivity of the N-
The IR spectra display the phenylethynyl CC absorption
band at ν
̃
1956 cm−1 for 4, 1952 cm−1 for 5, and 1962 cm−1 for
6, respectively. These IR bands are close to that found in 1,
indicating a M−(η2-CC) bonding mode in all three
complexes. The 1H NMR spectra show the γ-CH proton
resonance at δ 5.57 ppm for 4, δ 5.57 ppm for 5, and δ 5.00
ppm for 6. Note that the 19F NMR spectra display two groups
of resonance data for the respective compounds 4−6. This
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Figure 2. X-ray crystal structure of 2 with iPr of the Ar at L omitted for clarity. The disordered phenylethynyl group C(61)C(62)C(63)C(64)-
C(65)C(66)C(67)C(68) is shown with an occupation of 0.51796 and the related Ge(1)−C(61) and C(61)−C(62) bond lengths are given as
average values. Selected bond lengths (Å) and angles (deg): Ge(1)−N(1) = 1.927(4), Ge(1)−N(2) = 1.928(4), Ge(1)−C(61) = 1.93(3) (average
value), Ge(2)−N(3) = 1.927(4), Ge(2)−N(4) = 1.937(4), Ge(2)−C(51) = 1.929(6), Ge(1)−Ag(1) = 2.4732(10), Ge(2)−Ag(1) = 2.4731(10),
Ag(2)−C(70) = 2.101(6), Ag(2)−C(80) = 2.103(6), C(51)−C(52) = 1.202(7), C(61)−C(62) = 1.20(3) (average value); N(1)−Ge(1)−N(2) =
95.42(15), N(3)−Ge(2)−N(4) = 95.21(16), Ge(1)−Ag(1)−Ge(2) = 176.23(2), C(70)−Ag(2)−C(80) = 179.4(2).
Scheme 4. Formation of Compounds 4−6
Table 1. Summary of the 19F NMR Data for the MC6F5 (M =
Cu, Ag, Au) Entity in 1−6
19F NMR (δ, ppm)
compd
CuC6F5
AgC6F5
AuC6F5
1
−111.38, −160.09,
−161.51
2
−107.48, −159.58,
−161.88
3
4
−115.25, −159.92, −162.78
Figure 3. X-ray crystal structure of 3. Selected bond lengths (Å) and
angles (deg) (the data in brackets are for another independent
molecule): Ge(1)−N(1) = 1.919(4) [1.919(4)], Ge(1)−N(2) =
1.926(5) [1.926(4)], Ge(1)−C(31) = 1.926(5) [1.932(6)], Ge(1)−
Au(1) = 2.3683(6) [2.3461(7)], Au(1)−C(41) = 2.069(6) [2.058(7)],
C(31)−C(32) = 1.196(6) [1.215(8)]; N(1)−Ge(1)−N(2) =
95.48(19) [95.05(17)], Au(1)−Ge(1)−C(31) = 120.43(18)
[117.37(16)], Ge(1)−C(31)−C(32) = 173.3(6) [165.8(6)], C(31)−
C(32)−C(33) = 178.2(7) [179.7(8)], Ge(1)−Au(1)−C(41) =
176.64(14) [174.30(17)].
−111.83, −159.03,
a
−161.11
−105.01, −152.53,
b
−157.45
5
6
−112.40, −159.22, −107.49, −157.88,
−161.91
−114.79, −159.92,
−162.74
−161.91
−116.38, −123.31, 150.31,
−159.08, 161.87
a
b
Phenylethynyl group π-complexed CuC6F5 entity. Germylene-
bound CuC6F5 entity.
implies that the original CuC6F5 species and a newly bound
MC6F5 fragment actually exhibit different fluorine resonances.
On the basis of the 19F NMR data for 1−3, we were able to give
a reasonable assignment. As summarized in Table 1, for 4 one
group of resonances at δ −111.83, −159.03, and −161.11 ppm
is close to that for 1 and should correspond to the π-complexed
CuC6F5 species. Another group of resonances at δ −105.01,
−152.53, and −157.45 ppm is thus of the Ge-bound CuC6F5
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Figure 4. X-ray crystal structure of 5 with iPr of the Ar at L omitted for clarity. Selected bond lengths (Å) and angles (deg): Ge(1)−N(1) =
1.930(5), Ge(1)−N(2) = 1.944(5), Ge(1)−C(31) = 1.963(6), Ge(1)−Ag(1) = 2.4551(8), Ag(1)···Ag(1A) = 2.7073(9), Ag(1)−C(51) = 2.543(6),
Ag(1)−C(51A) = 2.237(7), Cu(1)−C(31) = 2.180(8), Cu(1)−C(32) = 2.316(10), Cu(1)···C(3) = 2.617, Cu(1)−C(41) = 1.925(10), N(1)−C(4)
= 1.330(8), N(2)−C(2) = 1.321(8), C(1)−C(2) = 1.512(9), C(2)−C(3) = 1.417(9), C(3)−C(4) = 1.392(9), C(4)−C(5) = 1.510(9), C(31)−
C(32) = 1.207(10); N(1)−Ge(1)−N(2) = 94.2(2), Ge(1)−C(31)−C(32) = 164.5(3), C(31)−C(32)−C(33) = 164.7(3), C(31)−Cu(1)−C(32) =
35.35(12), Ge(1)−Ag(1)−C(51) = 109.48(16), Ge(1)−Ag(1)−C(51A) = 138.76(17), C(51)−Ag(1)−C(51A) = 111.34(18). Symmetry code (A):
−x, −y + 2, −z + 1.
Figure 5. X-ray crystal structure of 6 with iPr of the Ar at L omitted for clarity. Selected bond lengths (Å) and angles (deg): Ge(1)−N(1) =
1.924(3), Ge(1)−N(2) = 1.921(1), Ge(1)−C(31) = 1.955(4), Ge(1)−Au(1) = 2.3625(4), Au(1)−C(41) = 2.056(4), Cu(1)−C(31) = 1.973(4),
Cu(1)−C(32) = 2.080(4), Cu(1)−C(3) = 2.343(3), Cu(1)−C(51) = 1.931(4), N(1)−C(2) = 1.329(5), N(2)−C(4) = 1.321(5), C(1)−C(2) =
1.506(5), C(2)−C(3) = 1.409(5), C(3)−C(4) = 1.417(5), C(4)−C(5) = 1.504(5), C(31)−C(32) = 1.221(5); N(1)−Ge(1)−N(2) = 94.80(12),
N(1)−Ge(1)−C(31) = 94.92(14), N(2)−Ge(1)−C(31) = 95.82(14), Ge(1)−Au(1)−C(41) = 175.21(11), Ge(1)−C(31)−C(32) = 164.4(3),
(31)−C(32)−C(33) = 164.2(4), C(31)−Cu(1)−C(32) = 34.94(14).
part. Similarly, in the spectrum of 5, the group of the
resonances at δ −112.40, −159.22, and −161.91 ppm is
assigned to the π-complexed CuC6F5 species, whereas another
group of resonances at δ −107.49, −157.88, and −161.91 ppm
is attributed to the Ge-bound AgC6F5 part. However, broad
resonances are observed for the latter group. This suggests an
aggregation of the AgC6F5 entity, as has been discussed in the
19F NMR spectrum of the compound {LGe[C(SiMe3)N2]-
(AgC6F5)2}2 due to the formation of an equilibrium by fast
transformation of the AgC6F5 species in solution.13 In the
spectrum of 6, the three resonances δ −114.78 (o-F), −159.91
(p-F), and −162.76 ppm (m-F) can be assigned to the CuC6F5
part. However, five resonances (δ −116.42 (o-F), −123.35 (o-
F), −150.31 (p-F), −159.08 (m-F), and −161.87 ppm (m-F))
were observed, which correspond to the Ge-bound AuC6F5
species due to hindered rotation probably induced by the bulky
iPr groups of the NAr substituents. However, this resonance
mode is quite different from the three resonances found in 3−
5. Although we performed VT NMR spectral measurements on
6 in CD2Cl2 from 20 to −50 °C, almost no change of this
resonance mode was found. Thus, we conclude that the
spectroscopic behavior of 6 in solution is not clear.
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Article
CD2Cl2 were degassed and dried over CaH2. 1H (400 MHz), 13C (100
MHz), and 19F NMR spectra (376 MHz) were recorded on a Bruker
Avance II 400 MHz spectrometer. Melting points of compounds were
The X-ray structural analysis of 5 clearly shows a novel
GeCuAg trimetallic hexanuclear compound with an additional
bonding of the AgC6F5 species at the germylene center (Figure
4). The AgC6F5 part aggregates to form a centrosymmetric
(AgC6F5)2 core. The Ag−CC F bond lengths are 2.237(7) and
measured in sealed glass tubes using a Buchi-540 instrument.
̈
Elemental analysis was performed on a Thermo Quest Italia SPA
EA 1110 instrument. Commercial reagents were purchased from
Aldrich, Acros, or Alfa-Aesar and used as received. (CuC6F5)4,15
6
5
2.543(6) Å and are longer than those of the terminal bond
distances in 2 (2.101(6) and 2.103(6) Å). In the similar
compound {LGe[C(SiMe3)N2](AgC6F5)2}2, the bridged Ag−
CC F bond lengths are 2.155(5) and 2.264(4) Å.13 These Ag−
32
AgC6F5·MeCN,31 and AuC6F5·SC4H4 were prepared according to
published procedures. LGeCCPh was synthesized using a one-pot
method, detailed as follows.
6
5
LGeCCPh. nBuLi (2 mL, 5 mmol, 2.5 M solution in n-hexane)
was added to a solution of LH (2.091 g, 5 mmol) in toluene (60 mL)
at −30 °C. The mixture was warmed to room temperature and stirred
for 12 h. After workup, the solution was cooled to −30 °C and then
slowly added to a precooled (−30 °C) suspension of GeCl2·(dioxane)
(1.160 g, 5 mmol) in toluene (30 mL) with stirring. After the mixture
was warmed to room temperature and stirred for an additional 12 h,
the orange-yellow suspension that formed was cooled to −30 °C again
before addition of LiCCPh which was freshly prepared from the
reaction of PhCCH (0.511 g, 5 mmol) with nBuLi (2 mL, 5 mmol,
2.5 M) in n-hexane (15 mL) at −30 °C to room temperature within 3
h. After the mixture was stirred for 20 h, all volatiles were removed
under reduced pressure and the residue was extracted with toluene.
The toluene extract was evaporated to dryness under reduced pressure
and further washed with cold n-hexane (2 × 1 mL) to give LGeC
C
bond lengths are remarkably longer than the Cu−C
C6F5
C6F5
bond length (1.925(10) Å). The Ge−Ag bond length is
2.4551(8) Å and is comparable to those in 2. However, the
bound AgC6F5 species at the Ge atom appears to give rise to a
significant change of the bond parameters around the Cu atom,
and longer Cu−CCC (2.180(8) and 2.316(10) Å) as well as
remarkably longer Cu−Cγ‑C (2.617 Å) bond lengths are
observed in comparison to those in 1. This indicates that in
5 the aforementioned C3N2Ge ring···CuC6F5 π complexation is
mainly adopted.
The structure of 6 shows a GeCuAu trimetallic compound
with a terminally bound AuC6F5 species at the Ge center
(Figure 5). The Au−CC F bond length (2.056(4) Å) can be
compared with those in 3 (2.058(7)−2.069(6) Å), but it is
longer than the Cu−CC F bond length (1.931(4) Å). The Ge−
Au bond length (2.3625(4) Å) is similar to that in 3. This Ge−
AuC6F5 bound part seems to have no great effect on the
bonding parameters around the Cu center. Cu−CC F (1.931(4)
Å), Cu−CCC (1.973(4) and 2.080(4) Å), and Cu−Cγ‑C
(2.343(3) Å) bond lengths close to those found in 1 suggest
a relatively strong F5C6Cu−γ-CH interaction.
1
6
5
CPh as a golden yellow crystalline solid (2.66 g, 90%). The H NMR
spectral data are the same as those obtained from the reaction of L′Ge
(L′ = HC[C(CH2)N-2,6-iPr2C6H3][C(Me)N-2,6-iPr2C6H3] with
6
5
PhCCH.14 IR (KBr plate, Nujol mull, cm−1): ν
2117 (w, CC).
̃
LGe(CCPh)CuC6F5 (1). In a glovebox, a solution of (CuC6F5)4
(0.115 g, 0.125 mmol) in toluene (10 mL) was added to a stirred
solution of LGeCCPh (0.30 g, 0.5 mmol) in toluene (15 mL) at
room temperature. A quick color change from golden yellow to light
yellow was observed. The mixture was stirred for an additional 4 h.
After concentration to ca. 5 mL the solution was stored at −20 °C.
Two days later, X-ray-quality, light yellow crystals of 1·(toluene) were
6
5
1
formed and collected by filtration (0.35 g, 74%). Mp: 164 °C. H
CONCLUSION
■
NMR (400 MHz, C6D6, 298 K, ppm): δ 7.67−6.93 (m, 16 H, C6H3,
C6H5, MePh), 5.75 (s, 1 H, γ-CH), 3.40 (br, 2 H), 3.17 (br, 2 H)
(CHMe2), 2.11 (s, 3 H, PhMe), 1.71 (s, 6 H, CMe), 1.24, 1.21 (d,
overlapped, 18 H), 0.96 (d, 6 H) (CHMe2). 13C NMR (100 MHz,
C6D6, 298 K, ppm): δ 173.05 (CN), 145.77, 142.58, 139.53, 137.64,
132.14, 129.08, 128.87, 128.57, 128.31, 129.19, 127.92, 127.68, 125.44,
125.13, 124.06 (C6H3, C6H5, C6F5, PhMe), 121.18, 115.58 (CCPh),
88.79 (γ-C), 29.45, 29.31, 27.37, 24.33, 24.08, 22.96, 22.88, 21.18
(CMe, CHMe2, PhMe). 19F NMR (376 MHz, C6D6, 298 K, ppm): δ
−111.38 (m, 2 F, o-F), −160.09 (m, 1 F, p-F), −161.51 (m, 2 F, m-F).
In summary, we have presented reactions of the β-diketiminato
ligand stabilized (phenylethynyl)germylene LGeCCPh with
pentafluorophenylcopper(I), -silver(I), and -gold(I) complexes.
We isolated and structurally characterized a series of group 11
metal(I)−germylene complexes LGe(CCPh)CuC6F5 (1),
[(LGeCCPh)2Ag]+[Ag(C6F5)2]− (2), LGe(CCPh)-
AuC6F5 (3), and LGe(CCPh)(CuC6F5)(MC6F5) (M = Cu
(4), Ag (5), Au (6)). The formation of compounds 1−3 reveals
routes of the MC6F5 species at the different donor sites of
LGeCCPh. This is obviously due to slightly different Lewis
acidic species of the pentafluorophenylcopper(I), -silver(I), and
-gold(I) complexes as acceptors. The donor molecule
coordination dependent properties of these complexes imply
the difference in their Lewis acidities.15−18,31,32 However,
detailed studies on this chemistry have been reported to a much
lesser extent.33 Compound 4 shows a bound CuC6F5 species
not only at the germylene center but also at the phenylethynyl
group where the central C3N2Ge ring donor site is also
involved. However, the generation of 2, 3, 5, and 6 may indicate
a specific reactivity of the AgC6F5 or AuC6F5 species at the
germylene center.
IR (KBr plate, cm−1): ν
was used for elemental analysis. Anal. Calcd for C43H46CuF5GeN2 (Mr
= 822.02): C, 62.83; H, 5.64; N, 3.41. Found: C, 62.56; H, 5.43; N,
3.39.
̃
1957 (w, CC). The crystalline solid of 1
[(LGeCCPh)2Ag]+[Ag(C6F5)2]− (2). In a glovebox, LGeCCPh
(0.12 g, 0.2 mmol) and AgC6F5·MeCN (0.06 g, 0.2 mmol) were mixed
in a brown vial and toluene (2.5 mL) was added. The mixture was
stirred for 0.5 h, and then toluene (1 mL) was added until all solids
had dissolved. After it was stirred for an additional 1 h, the solution
was filtered to remove a small amount of precipitate. The filtrate was
layered with n-hexane (1 mL) and stored at −20 °C. Two days later,
yellow crystals of 2·2(toluene) were formed and collected by filtration
1
(0.12 g, 65%). Mp: 174 °C dec. H NMR (400 MHz, C6D6, 298 K,
ppm): δ 7.42−7.00 (m, 22 H, C6H3, C6H5), 4.98 (s, 2 H, γ-CH), 3.73
(sept, 3JHH = 6.8 Hz, 4 H), 3.30 (sept, 3JHH = 6.8 Hz, 4 H) (CHMe2),
1.47 (s, 12 H, CMe), 1.52 (d, 3JHH = 6.8 Hz, 12 H), 1.39 (d, 3JHH = 6.8
EXPERIMENTAL SECTION
3
3
■
Hz, 12 H), 1.16 (d, JHH = 6.8 Hz, 12 H), 1.02 (d, JHH = 6.8 Hz, 12
H) (CHMe2). 13C NMR (100 MHz, C6D6, 298 K, ppm): δ 168.90
(CN), 146.38, 143.34, 138.31, 131.94, 128.89, 128.59, 128.45, 127.82,
127.68, 125.29, 124.75 (C6H3, C6H5, C6F5), 123.55, 104.72 (CCPh),
100.30 (γ-C), 29.72, 28.65, 27.68, 24.62, 24.49, 23.81, 23.11 (CMe,
CHMe2). 19F NMR (376 MHz, C6D6, 298 K, ppm): δ −107.48 (m, 4
F, o-F), −159.58 (m, 2 F, p-F), −161.88 (m, 4 F, m-F). IR (KBr plate,
Materials and Methods. All syntheses and manipulations were
carried out on a Schlenk line or in an argon-filled MBraun glovebox
(typically oxygen and moisture were controlled at less than 1.2 ppm).
Toluene and n-hexane were dried by refluxing with sodium/potassium
benzophenone under N2 prior to use. The deuterated solvent C6D6
was degassed and dried over sodium/potassium alloy. CDCl3 and
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Nujol mull, cm−1): ν
used for elemental analysis. Anal. Calcd for C86H92Ag2F10Ge2N4 (Mr =
1732.68): C, 59.61; H, 5.35; N, 3.23. Found: C, 59.38; H, 5.23; N,
3.32.
̃
2145 (w, CC). The crystalline solid of 2 was
then added to a precooled (−20 °C) solution of AuC6F5·SC4H8 (0.14
g, 0.30 mmol) in toluene (10 mL) with stirring. A quick color change
from golden yellow to light yellow was observed. The mixture was
warmed to room temperature and stirred for an additional 1 h. After
concentration to ca. 5 mL the solution was stored at −20 °C. One
week later, X-ray-quality, light yellow crystals of 6·0.5(toluene) were
LGe(CCPh)AuC6F5 (3). In a glovebox, a solution of
AuC6F5·SC4H8 (0.18 g, 0.40 mmol) in toluene (5 mL) was added
to a stirred solution of LGeCCPh (0.24 g, 0.40 mmol) in toluene (5
mL) at room temperature. A quick color change from golden yellow to
light yellow was observed. The mixture was stirred for an additional 4
h, filtered, and stored at −20 °C. One week later, X-ray-quality,
colorless crystals of 3·0.75(toluene) were formed and collected by
filtration (0.29 g, 71%). Mp: 176 °C. 1H NMR (400 MHz, C6D6, 298
K, ppm): δ 7.40−6.96 (m, 14.8 H, C6H3, C6H5, PhMe), 4.96 (s, 1 H, γ-
CH), 3.74 (sept, 3JHH = 6.8 Hz, 2 H), 3.41 (sept, 3JHH = 6.8 Hz, 2 H)
1
formed and collected by filtration (0.21 g, 57%). Mp: 184 °C. H
NMR (400 MHz, C6D6, 298 K, ppm): δ 7.53−6.80 (m, 11 H, C6H3,
C6H5), 5.00 (s, 1 H, γ-CH), 3.50 (sept, 3JHH = 6.8 Hz, 2 H), 2.36 (sept,
3JHH = 6.8 Hz, 2 H) (CHMe2), 1.37 (s, 6 H, CMe), 1.72 (d, 3JHH = 6.8
3
Hz, 6 H), 1.02 (d, 3JHH = 6.8 Hz, 6 H), 0.83 (d, JHH = 6.8 Hz, 6 H),
3
0.42 (d, JHH = 6.8 Hz, 6 H) (CHMe2). 13C NMR (100 MHz, C6D6,
298 K, ppm): δ 170.47 (CN), 145.27, 144.16, 137.38, 129.38, 129.07,
128.83, 128.72, 128.60, 128.43, 128.30, 127.14, 127.07, 125.43, 125.02
(C6H3, C6H5, C6F5), 125.18, 124.73 (CCPh), 100.08 (γ-C), 31.71,
30.25, 28.11, 24.68, 24.64, 24.17, 23.85, 23.59, 22.79 (CMe, CHMe2).
19F NMR (376 MHz, C6D6, 298 K, ppm): δ −114.78 (br, 2 F, o-F),
−159.91 (br, 1 F, p-F), −162.76 (br, 2 F, m-F) (AuC6F5), −116.42 (m,
1 F, o-F), −123.35 (m, 1 F, o-F), −150.31 (m, 1 F, p-F), −159.08 (m,
(CHMe2), 2.11 (s, 2.2 H, PhMe), 1.46 (s, 6 H, CMe), 1.60 (d, 3JHH
=
3
3
6.8 Hz, 6 H), 1.43 (d, JHH = 6.8 Hz, 6 H), 1.16 (d, JHH = 6.8 Hz, 6
3
H), 1.05 (d, JHH = 6.8 Hz, 6 H) (CHMe2). 13C NMR (100 MHz,
C6D6, 298 K, ppm): δ 169.63 (CN), 146.23, 143.70, 138.02, 132.03,
129.07, 128.98, 128.73, 128.44, 128.30, 127.91, 127.68, 125.43, 125.15,
124.71, 123.27 (C6H3, C6H5, C6F5, PhMe), 104.83, 101.37 (CCPh),
100.39 (γ-C), 29.83, 28.73, 27.64, 24.44, 23.75, 23.23, 21.16 (CMe,
CHMe2, PhMe). 19F NMR (376 MHz, C6D6, 298 K, ppm): δ −115.25
(m, 2 F, o-F), −159.92 (m, 1 F, p-F), −162.78 (m, 2 F, m-F). IR (KBr
1 F, m-F), −161.87 (m, 1 F, m-F) (CuC6F5). IR (KBr plate, cm−1): ν
̃
1962 (w, CC). Anal. Calcd for C52.5H50AuCuF10GeN2 (6·0.5-
(toluene), Mr = 1232.11): C, 51.18; H, 4.09; N, 2.27. Found: C, 50.82;
H, 4.13; N, 2.37.
plate, Nujol mull, cm−1): ν
̃
2135 (w, CC). Anal. Calcd for
X-ray Crystallographic Analyses of Complexes 1−3, 5, and
6. Crystallographic data for 1·(toluene,) 32·1.5(toluene), 5·(toluene),
and 6·0.5(toluene) were collected on an Oxford Gemini S Ultra
system, and the data for 2·2(toluene) was obtained on a Rigaku R-Axis
Spider IP system. In all cases graphite-monochromated Mo Kα
radiation (λ = 0.71073 Å) was used. Absorption corrections were
applied using the spherical harmonics program. Structures were solved
by direct methods (SHELXS-96)34 and refined against F2 using
SHELXL-97.35 In general, the non-hydrogen atoms were located by
difference Fourier synthesis and refined anisotropically, and hydrogen
atoms were included using the riding model with Uiso tied to the Uiso
values of the parent atoms unless otherwise specified. In 1·(toluene),
the two toluene molecules were located and refined isotropically with
respective occupations of 0.5. In 2·2(toluene), one of the phenyl-
ethynyl groups was disordered, treated in a splitting mode, and refined
isotropically. In addition, three toluene molecules were located, one of
which was disordered, treated in a splitting mode, and refined
isotropically, while the other two toluene molecules were refined
isotropically, both with the respective occupations of 0.5. In
32·1.5(toluene), two independent molecules of 3 were disclosed, in
which one of the isopropyl groups of the aryl substituent was
disordered, treated in a splitting mode, and refined isotropically.
Furthermore, the two toluene molecules were located and refined
isotropically, one of which with an occupation of 0.5 was seriously
disordered and refined isotropically. It was not possible to realize
hydrogen atom addition. In 5·(toluene), the toluene molecule was
seriously disordered and could not be treated upon hydrogen atom
addition. In 6·0.5(toluene), the toluene molecule was disordered,
treated in a splitting mode, and refined isotropically. For this toluene
molecule, it was not possible to realize hydrogen atom addition. Cell
parameters, data collection, and structure solution and refinement
details are given in Table 1s (Supporting Information).
C48.25H52AuF5GeN2 (3·0.75(toluene), Mr = 1024.54): C, 56.56; H,
5.12; N, 2.73. Found: C, 56.24; H, 5.18; N, 2.67.
LGe(CCPh)(CuC6F5)2 (4). In a glovebox, a solution of LGeC
CPh (0.12 g, 0.20 mmol) in toluene (5 mL) was cooled to −20 °C and
added to a precooled (−20 °C) solution of (CuC6F5)4 (0.09 g, 0.10
mmol) in toluene (5 mL). The mixture was stirred for 5 min, and a
quick color change from golden yellow to light yellow was observed.
The solution was stored at −20 °C. Two days later, a light yellow solid
of 4 was formed and collected (0.09 g, 43%). Mp: 154 °C dec. Due to
the very poor solubility of 4 in organic solvents, the 1H and 19F NMR
data were only obtained from in situ measurement of the NMR-tube
reaction of LGeCCPh with 1 equiv of (CuC6F5)2·(dioxane) in
C6D6. The 13C NMR data were not available. H NMR (400 MHz,
1
C6D6, 298 K, ppm): δ 7.88−6.93 (m, 11 H, C6H3, C6H5), 5.57 (s, 1 H,
γ-CH), 3.35 (s, 8 H, dioxane-H), 2.84 (br, 4 H, CHMe2), 1.49 (s, 6 H,
3
3
CMe), 1.36 (d, JHH = 6.4 Hz, 6 H), 1.07 (d, JHH = 6.4 Hz, 12 H),
3
0.74 (d, JHH = 6.4 Hz, 6 H) (CHMe2). 19F NMR (376 MHz, C6D6,
298 K, ppm): δ −111.87 (m, 2 F, o-F), −159.03 (t, 1 F, p-F), −161.10
(m, 2 F, m-F) (π-complexed CuC6F5), −105.06 (m, 2 F, o-F), −152.52
(t, 1 F, p-F), −157.45 (m, 2 F, m-F) (Ge−CuC6F5). IR (KBr plate,
cm−1): ν
̃
1956 (w, CC). Anal. Calcd for C49H46Cu2F10GeN2 (Mr =
1052.62): C, 55.91; H, 4.40; N, 2.66. Found: C, 55.62; H, 4.48; N,
2.61.
LGe(CCPh)(CuC6F5)(AgC6F5) (5). In a glovebox, 1 (0.16 g, 0.2
mmol) and AgC6F5·MeCN (0.06 g, 0.2 mmol) were mixed in a brown
vial and toluene (2.5 mL) was added. The mixture was stirred for 0.5
h, and then toluene (1 mL) was added until all solids had dissolved.
After it was stirred for an additional 1 h, the solution was filtered to
remove a small amount of precipitate. The filtrate was layered with n-
hexane (1 mL) and stored at −20 °C. Two days later, light yellow
crystals of 5·(toluene) were formed and collected by filtration (0.17 g,
72%). Mp: 147 °C dec. 1H NMR (400 MHz, CDCl3, 298 K, ppm): δ
= 7.55−7.17 (m, 27 H, C6H3, C6H5, PhMe), 5.57 (br, 2 H, γ-CH), 3.59
(br, 2 H), 3.10 (br, 6 H) (CHMe2), 2.36 (s, 3 H, PhMe), 1.96 (s,
ASSOCIATED CONTENT
■
3
S
* Supporting Information
overlapped, 12 H, CMe), 2.09 (br, 12 H), 1.37 (d, JHH = 6.4 Hz, 12
3
3
H), 1.27 (d, JHH = 6.4 Hz, 12 H), 1.13 (d, JHH = 6.4 Hz, 12 H)
(CHMe2). The 13C NMR spectrum did not give reliable data due to
limited solubility. 19F NMR (376 MHz, C6D6, 298 K, ppm): δ
−107.50 (br, 4 F, o-F), −157.78 (br, 2 F, p-F), −161.58 (br, 4 F, m-F)
(AgC6F5), −112.44 (m, 4 F, o-F), −159.22 (br, 2 F, p-F), −161.58 (br,
CIF files and a table giving crystallographic data for 1−3, 5, and
6 and figures giving NMR spectra of 1−6. This material is
available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
4 F, m-F) (CuC6F5). IR (KBr plate, cm−1): ν
̃
1952 (w, CC). The
■
crystalline solid of 5 was used for elemental analysis. Anal. Calcd for
C49H46AgCuF10GeN2 (Mr = 1096.94): C, 53.65; H, 4.23; N, 2.55.
Found: C, 53.53; H, 4.28; N, 2.47.
Corresponding Author
*E-mail: hpzhu@xmu.edu.cn.
Notes
LGe(CCPh)(CuC6F5)(AuC6F5) (6). In a glovebox, a solution of 1
(0.25 g, 0.30 mmol) in toluene (15 mL) was cooled to −20 °C and
The authors declare no competing financial interest.
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Article
(18) Doshi, A.; Sundararaman, A.; Venkatasubbaiah, K.; Zakharov, L.
ACKNOWLEDGMENTS
■
N.; Rheingold, A. L.; Myahkostupov, M.; Piotrowiak, P.; Jakle, F.
̈
This work was supported by the 973 Program
(2012CB821704), the National Nature Science Foundation of
China (91027014 and 20972129), and the Innovative Research
Team Program (IRT1036 and J1030415).
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