Synthesis of phosphorus- and sulfur-stabilized carbone (Me)Ph2P→C←SPh2(= NMe)

Article abstract of DOI:10.1080/10426507.2015.1114488

Iminosulfane(phosphane)carbon(0) (iSPC) [(Me)Ph₂P→C←SPh₂(= NMe): 1] is generated by the deprotonation of corresponding cationic salt 1·H, which is obtained from the reaction of iminosulfonium methylide with Ph₂PCl and subsequent P-methylation. Density functional theory calculations reveal that the electronic structure of 1 has two lone pairs of electrons at the carbon center. First and second proton affinity values are theoretically calculated to be 287.2 and 187.0 kcal mol^-1, respectively. The highest occupied molecular orbital (HOMO) energy level of 1 is higher energy than that of bis(iminosulfane)carbon(0) (BiSC: [(MeN =)Ph₂S→C←SPh₂(= NMe)]). The reactivities of these lone pairs of electrons are demonstrated by the C-diaurated complex.

Full text of DOI:10.1080/10426507.2015.1114488

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Synthesis of phosphorus- and sulfur-stabilized
carbone (Me)Ph2P→C←SPh2(= NMe)
Tomohito Morosaki & Takayoshi Fujii
To cite this article: Tomohito Morosaki & Takayoshi Fujii (2016) Synthesis of phosphorus- and
sulfur-stabilized carbone (Me)Ph2P→C→SPh2(= NMe), Phosphorus, Sulfur, and Silicon and the
Related Elements, 191:2, 159-162, DOI: 10.1080/10426507.2015.1114488
To link to this article: http://dx.doi.org/10.1080/10426507.2015.1114488
Accepted author version posted online: 03
Nov 2015.
Submit your article to this journal
Article views: 21
View related articles
View Crossmark data
Full Terms & Conditions of access and use can be found at
http://www.tandfonline.com/action/journalInformation?journalCode=gpss20
Download by: [University of Illinois, Chicago]
Date: 23 February 2016, At: 11:35

PHOSPHORUS, SULFUR, AND SILICON
, VOL. , NO. , –
http://dx.doi.org/./..
Synthesis of phosphorus- and sulfur-stabilized carbone (Me)PhP→C←SPh(= NMe)
Tomohito Morosaki and Takayoshi Fujii
Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba, Japan
ABSTRACT
ARTICLE HISTORY
Received  August 
Accepted  October 
Iminosulfane(phosphane)carbon(0) (iSPC) [(Me)Ph2P→C←SPh2(= NMe): 1] is generated by the deprotona-
tion of corresponding cationic salt 1·H, which is obtained from the reaction of iminosulfonium methylide
with Ph2PCl and subsequent P-methylation. Density functional theory calculations reveal that the elec-
tronic structure of 1 has two lone pairs of electrons at the carbon center. First and second proton affin-
ity values are theoretically calculated to be 287.2 and 187.0 kcal mol−1, respectively. The highest occupied
molecular orbital (HOMO) energy level of 1 is higher energy than that of bis(iminosulfane)carbon(0) (BiSC:
[(MeN =)Ph2S→C←SPh2(= NMe)]). The reactivities of these lone pairs of electrons are demonstrated by the
C-diaurated complex.
KEYWORDS
Carbones; electronic
structure; gold
GRAPHICAL ABSTRACT
These iSPC derivatives E–G are synthesized by the reaction
of iminosulfonium salt with corresponding triarylphosphonium
ylide.6 However, the synthetic strategies of iSPC for further
structural modification remained limited by the fact that the
synthetic equivalent of iminosulfonium ligand is electrophilic
iminosulfonium salt [FPh2SNMe]BF4. In our previous work, we
have reported that the reaction of iminosulfonium ylide 4 with
carbonyl compounds affords the corresponding stable iminosul-
fonium ylide.7 These results prompted us to examine the reac-
tion of 4 with electrophilic phosphine chloride and subsequent
P-methylation which might lead to the formation of protonated
salt of iSPC 1. We believe that an improvement in the synthetic
methods and structural diversity of iSPCs might extend their
utility into the realm of organometallic chemistry and cataly-
sis. Here we report the development of a new synthetic protocol
for the preparation of iSPC 1 with the alkyl substituted phos-
phine ligand using nucleophilic iminosulfonium methylide, and
the synthesis of its C-diaurated complex 2 in order to clarify its
four-electron donor ability. We also describe the comparison of
1 to previously reported A–G.
Introduction
Carbones consist of two strong electron-donating ligands,
such as phosphanes in carbodiphosphorane (termed as
“bis(phosphane)carbon(0) (BPC: A)” in our study) coordi-
nated to the central zero-valent carbon atom, which main-
tains its four valence electrons in two orthogonal lone pair
orbitals. Therefore, it is also described as a carbon complex
(Figure 1).1–4
Recently, we reported the syntheses and reactivities of
two-chalcogen stabilized carbones (bis(iminosulfane)carbon(0)
(BiSC: B), iminosulfane(sulfane)carbon(0) (iSSC: C), and
iminosulfane(selenane)carbon(0) (iSSeC: D)), that are four-
electron donors.5 Furthermore, we reported the syntheses
of phosphorus- and sulfur-stabilized carbones (iminosul-
fane(phosphane)carbon(0) (iSPC: E–G)) bearing triaryl phos-
phane ligand.6 Among them, G is the first thermally and mois-
ture stable carbone stabilized by phosphorus and sulfur ligand.
In these work we revealed that the electron-donating ability of
central carbon in carbones can be tuned by the replacement of
the ligand.
CONTACT Takayoshi Fujii
- Japan.
fujii.takayoshi@nihon-u.ac.jp
Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba
©  Taylor & Francis Group, LLC

160
T. MOROSAKI AND T. FUJII
Figure . Molecular structures of A–G.
Figure . HOMO (left) and HOMO- (right) of iSPC 1.
Results and discussion
frontier orbitals reveals that the central carbon atom of 1 has
two lone pair orbitals in the highest occupied molecular orbital
(HOMO: nπ ; HOMO–1: nσ ; Figure 2). Natural bond orbital
According to our previous reports, the iminosulfonium salt
3 was synthesized by the reaction of methyldiphenyl-λ6-
sulfanenitrile with MeTfO in dichloromethane at −20°C.7 The
reaction of iminosulfonium ylide 4 with Ph2PCl and subsequent
addition of MeOTf affords the corresponding monoprotonated
salt 1·H in 35% yield (Scheme 1). The formation of 1·H was
characterized by 1H, 13C, and 19F NMR spectroscopy and X-ray
crystallographic analysis.8 iSPC 1 is cleanly generated by depro-
tonation of 1·H with sodium amide or potassium hexamethyld-
isilazide in THF or C6D6. 1 is rapidly hydrolyzed to phosphine
oxide 5 and sulfimide 6 under air in the solution (Scheme 1).
In addition, passing 1·H through an ion-exchange resin col-
umn (IRA-410, OH− form) affords the hydrolyzed products. We
assumed that 1 is hydrolyzed by the attack at the cationic phos-
phorus center by H2O or OH−.
C
C
(NBO) analyses indicate that nσ has an s character (33%), indi-
C
cating a hybridization close to sp2, whereas the nπ lone pair
C
has 100% p character. The central carbon atom of 1 bears a
large negative charge (−1.38 e), which is similar to that of BPC
(A: −1.55 e), BChCs (B: −1.24 e; C: −1.20 e; D: −1.25 e), and
iSPCs (E–G: −1.38 e).1,5b,6 The Wiberg bond index value of
iSPC for the P→C (1.25) is lower than that of S→C (1.31), which
is similar to the trend observed in iSPCs (P→C: E: 1.26, F: 1.24,
G: 1.22; S→C: E: 1.30, F: 1.31, G: 1.34).6
To verify the carbone character, we calculated the first and
second proton affinities (PA(1) and PA(2)) of 1 and compared
them with the theoretically predicted values for the PAs of car-
bones A–G (Table 1). The theoretically predicted PA(1) of 1 is
quite high, suggesting their strong basic character. The calcula-
tions predict that iSPC 1 has a higher PAs than BiSC B, whereas
In the 13C NMR spectra, the central carbon atom of 1 appears
as a doublet (21.7 ppm, 1JPC = 37 Hz), which is shifted to a lower
1
field compared with the cationic salt (1·H: 12.8 ppm, JPC
=
62 Hz), while the signal is slightly shifted to a higher field com-
pared with the iSPCs (E: 23.1 ppm, 1JPC = 62 Hz; F: 23.0 ppm,
1JPC = 58 Hz; G: 23.6 ppm, 1JPC = 68 Hz).6 These values sug-
gest the carbone character of 1.9 In the 31P NMR spectra, the
signal of 1 (−8.29 ppm) is significantly shifted to a higher field
than that of cationic salt 1·H (12.5 ppm), iSPC (E: −2.64 ppm;
F: −3.51 ppm; G: −1.39 ppm) and BPC (−2.14 ppm).6,10 Unfor-
tunately, all attempts to grow X-ray quality single crystals for
diffraction analysis of 1 were unsuccessful.
Table . Calculated energy levels of the HOMO, HOMO– and proton affinities (PAs)
of 1 and A–G at BPW/–G(d,p).
PA()
PA()
HOMO (eV) HOMO- (eV) (kcal mol−
)
(kcal mol−
)

−.
−.
−.
−.
−.
−.
−.
−.
−.
−.
−.
−.
−.
−.
−.
−.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
A
Bb
Cb
Db
E
To gain insight into the electronic structures of 1, den-
sity functional theory (DFT) calculations at the B3PW91/6–
311G(d,p) level are performed (Figure 2).11,12 Inspection of the
F
G
Scheme . Synthesis of 1 and molecular structure of 1·H. Hydrogen atoms (except for that on Ccenter) and TfO anion are omitted for clarity. Reagents and conditions (yields):
(a) LDA ( equiv), THF, −°C  h; (b) PhPCl, THF, −°C,  h, then HO (%); (c) NaNH or KHMDS, THF or CD, −°C to RT, . h (%); (d) RT, air,  h; 5 (%), 6 (%);
(e) Amberlite IRA- ion-exchange resin (OH− form), MeOH, RT; 5 (%), 6 (%), LDA = lithium diisopropylamide, THF = tetrahydrofuran.

PHOSPHORUS, SULFUR, AND SILICON
161
smaller than BPC A. The PA(2) of 1 is much smaller than the
PA(1). The same observation has been reported by Frenking
et al.1d PA(1) is mainly determined by the energy level of the
highest lying occupied σ orbital of neutral carbones 1, whereas
the PA(2) is mainly determined by the highest lying occupied π
orbital of protonated 1·H.
Experimental
The reactions were carried out under an atmosphere of dry
argon. Reagents were purchased reagent grade from commercial
suppliers and used without further purification. H, 13C{1H},
1
19F{1H}, and 31P{1H} NMR spectroscopies were recorded on a
Bruker Avance 500 MHz spectrometer. H and 13C{1H} NMR
1
We attempted to ascertain whether the central carbon of
iSPC 1 could actually be employed as a four-electron donor.
The desired diaurated complex 2 is efficiently obtained by treat-
ing 1 with 2 equivalents of Ph3PAuCl/AgBF4. This demon-
strates the four-electron donor propeties of iSPC 1. In the 31P
NMR spectra, the signal for 2 (28.6, 35.0 ppm) is observed as
a singlet. These signals are similar to those of the diaurated
complexes of A, E, and G.6,10 Single crystal X-ray diffraction
analysis of 2 confirmed the complexation of the carbon cen-
ter of 1 to the Au(I) moieties (Scheme 2). The C→Au bond
chemical shifts (δ) in CDCl3 are given in ppm relative to
Si(CH3)4, coupling constants (J) in Hz. 1H and 13C{1H} NMR
chemical shifts (δ) in C6D6 are calibrated to the residual proton
resonance of the solvent (C6D6: δH = 7.16, δC = 128.06). Chem-
ical shifts for 19F{1H} and 31P{1H} NMR spectroscopy were ref-
erenced to an external standard (C6H5CF3; δ = −63.7, 85%
F
H3PO4; 0.0). Iminosulfonium salt 3 was prepared according to
the literature.7
˚
distances of 2 (2.111 and 2.117 A) are similar to those of
Compound 1·H
˚
diaurated carbone complexes (A·(AuCl)2: 2.074 and 2.078 A;
To a suspension of iminosulfonium salt 3 (379 mg, 1.0 mmol)
in THF (20 mL) at −78°C was added LDA (1.5 mL, 2.0 M
solution in THF/heptane/ethylbenzene, 3.0 mmol). After stir-
ring for 1 h at RT, the solution was cooled to −78°C and a cold
THF solution (10 mL, −78°C) of Ph2PCl (0.2 mL, 0.5 mmol)
was added. The resulting solution was stirred overnight. Then,
MeTfO (0.11 mL, 1.0 mmol) was added and the reaction mix-
ture was slowly warmed to room temperature over 2 h. The reac-
tion was quenched via the addition of H2O (10 mL). The water
phase was extracted with Et2O (20 mL × 3). The organic phase
was dried (MgSO4) and filtered with DCM. Solvent removal
and recrystallization from MeOH/Et2O afforded 1·H (88 mg,
30%) as colorless crystal. The solid product of 1·H suitable for
X-ray analysis was recrystallized in MeCN/Et2O to yield
colorless crystals.
˚
A·(AuPPh3)(AuCl): 2.080 and 2.127 A; Ph3PCC(OEt)2·(AuCl)2:
4,6,10,13
˚
˚
2.080 and 2.103 A; G·(AuPPh3)2: 2.118 and 2.127 A).
˚
The Au–Au distance of 2 (2.929 A) is the slightly longer
˚
than that of G·(AuPPh3)2 (2.910 A), while the shorter than
˚
˚
those of diaurated carbone complexes (A·(AuCl)2: 3.143 A;
˚
A·(AuPPh3)(AuCl): 3.127 A; Ph3PCC(OEt)2·(AuCl)2: 2.952 A;
4,6,10,13
˚
E·(AuPPh3)2: 3.005 A).
This distance is within the range
observed for Au–Au interactions (2.50–3.50 A).14 The P→C (2:
˚
˚
˚
1.789 A) and S→C (2: 1.728 A) bond distances are longer than
˚
˚
those in 1·H (P→C: 1.721 A, S→C: 1.660 A). The Au←C→Au
bond angle (87.7°) in diaurated complex 2 is wider than that
of G·(AuPPh3)2 (86.5°), while narrower than those of diau-
rated carbone complexes (A·(AuCl)2: 98.4°; A·(AuPPh3)(AuCl):
96.1°: Ph3PCC(OEt)2·(AuCl)2: 89.7°).4,6,10,13 The P→C←S
angles of 2 (112.0°) is narrower than those in 1·H (122.0°) and
G·(AuPPh3)2 (115.6°).6
1
1·H: m.p. 161–162°C; H NMR (500 MHz, CDCl3) δ 2.29
2
2
(d, JPH = 13.5 Hz, 3H), 2.62 (s, 3H), 3.68 (d, JPH = 5.5 Hz,
1H), 7.47–7.52 (m, 10H), 7.59 (td, JHH = 6.2 Hz, 1.8 Hz, 2H),
7.67 (dd, JPH = 13.5 Hz, 7.5 Hz, 4H), 7.99 (dd, JHH = 7.5 Hz,
1.8 Hz, 4H); 13C NMR (100 MHz, CDCl3) δ 12.8 (d, JCP
=
62.4 Hz, PCH), 18.2 (d, JCP = 108.7 Hz, PCH3), 30.1 (s, NCH3),
124.5 (d, JCP = 92.0 Hz, PCipso), 127.2, 129.5 (d, 2JCP = 12.7 Hz),
129.9, 131.9 (d, 3JCP = 10.9 Hz), 133.3, 133.5 (d, 4JCP = 2.90 Hz),
139.2 (SCipso); 19F NMR (470 MHz, CDCl3) δ –79.1; 31P NMR
(202 MHz, CDCl3) δ 12.46.
Compound 1·H crystallizes in the orthorhombic space group
P212121 (No. 19), C 28 H 27 F 3 N O 3 P S 2, M = 577.6 g mol−1
,
˚
crystal dimensions 0.27 × 0.17 × 0.10 mm, a = 10.896(2) A,
3
˚
˚
˚
b = 13.246(3) A, c = 19.195(6) A, V = 2770.6(12) A , Z = 4,
θ
= 3.19°, θ
= 27.46°, ρ = 1.385 g·cm−1, μ (MoKα) =
min
max
Scheme . Synthesis and molecular structure of 2. Hydrogen atoms, BF anions,
and solvent molecules (acetone) are omitted for clarity. Reagents and conditions
(yields): PhPAuCl ( equiv) AgBF ( equiv), THF, −°C,  h; (%).
0.301 mm−1, F000 = 1200, –14 ࣘ h ࣘ 13, –17 ࣘ k ࣘ 17, –24 ࣘ l
ࣘ 24, 27323 reflections measured, 6316 unique (Rint = 0.0873),
R1 = 0.0563 (I > 2.0σ (I)), Rw = 0.1522 (all data), GooF =
1,043, 349 parameters, 0 restraints.
Conclusions
In conclusion, we have successfully synthesized iSPC derivative
1 bearing a methyl(diphenyl)phosphane ligand. The reactivities
Compound 1
of lone pairs at central carbon of 1 predicted by the DFT calcu- To a mixture of 1·H (115 mg, 0.2 mmol) and NaNH2 (15.6 mg,
lations are demonstrated by the diaurated complex 2. This study 0.4 mmol) was added THF (10 mL) at RT. The solution was
provides a new approach to the synthesis of various iSPC deriva- stirred for 0.5 h. After removal of all the volatiles under vacuum,
tives bearing various phosphane ligand.
carbone 1 was extracted with Et2O (10 mL × 3). Concentration

162
T. MOROSAKI AND T. FUJII
of the organic phase in vacuum afforded the desired product as
a yellow powder (95 mg, 97%).
Shimizu, T.; Krapp, A.; Pandey, K. K.; Parameswaran, P.; Chem. Soc.
Rev. 2014, 43, 5106-5139. (i) Frenking, G.; Angew. Chem. 2014, 126.
6152-6158; Angew. Chem. Int. Ed. 2014, 53, 6040-6046.
1: 1H NMR (500 MHz, C6D6) δ 1.78 (d, 2JPH = 12.5 Hz, 3H),
3.01 (s, 3H), 6.89–6.92 (m, 2H), 6.99–7.03 (m, 10H), 7.72–7.78
(m, 4H), 8.48–8.50 (m, 4H); 13C NMR (125 MHz, C6D6) δ 17.3
(d, 1JCP = 50.3 Hz, PCH3), 21.7 (d, 1JCP = 36.5 Hz, PCS), 31.0
(s, NCH3), 128.2, 128.3, 128.4 (d, JCP = 1.3 Hz), 129.5, 130.2 (d,
JCP = 2.5 Hz), 131.6 (d, JCP = 10.1 Hz), 136.2 (d, JCP = 94.3 Hz,
PCipso), 149.1 (d, JCP = 13.8 Hz, SCipso); 31P NMR (202 MHz,
C6D6) δ −8.29.
2. (a) Kolodiazhnyi O. I., Tetrahedron 1996, 52, 1855-1929.
(b) Kolodiazhnyi, O. I.; Phosphorus Ylides: Chemistry and Application
in Organic Synthesis, Wiley-VCH, Weinheim, 1999. (c) Stallinger, S.;
Reitsamer, C.; Schuh, W.; Kopacka, H.; Wurst, K.; Peringer, P.; Chem.
Commun. 2007, 510-512. (d) Reitsamer, C.; Stallinger, S.; Schuh, W.;
Kopacka, H.; Wurst, K.; Obendorf, D.; Peringer, P.; Dalton Trans.
2012, 41, 3503-3514. (e) Petz, W.; Coord. Chem. Rev. 2015. 291, 1-27.
3. For cyclic bis(phosphane)carbon(0) derivatives, see:(a) Schmidbaur,
H.; Costa, T.; Milewski-Mahrla, B.; Schubert, U.; Angew. Chem.
Int. Ed. Engl. 1980, 19, 555-556. (b) Schmidbaur, H.; Costa, T.;
Chem. Ber. 1981, 114, 3063-3069. (c) Schubert, U.; Kappenstein, C.;
Milewski-Mahrla, B.; Schmidbaur, H.; Chem. Ber. 1981, 114, 3070-
3078. (d) Marrot, S.; Kato, T.; Gornitzka, H.; Baceiredo, A.; Angew.
Chem. 2006, 118, 2660-2663. Angew. Chem. Int. Ed. 2006, 45, 2598-
2601.
4. (a) Alcarazo, M.; Lehmann, C. W.; Anoop, A.; Thiel, W.; Fürstner, A.;
Nat. Chem. 2009, 1, 295-301. (b) Alcarazo, M.; Suárez, R. M.; God-
dard, R.; Fürstner, A.; Chem. Eur. J. 2010, 16, 9746-9749. (c) Alcarazo,
M.; Dalton Trans. 2011, 40, 1839-1845. (d) Schmidbaur, H.; Schier, A.;
Angew. Chem. 2013, 125, 187-197; Angew. Chem. Int. Ed. 2013, 52, 176-
186.
5. (a) Fujii, T.; Ikeda, T.; Mikami, T.; Suzuki, T.; Yoshimura, T.; Angew.
Chem. 2002, 114, 2688-2690; Angew. Chem. Int. Ed. 2002, 41, 2576-
2578. (b) Morosaki, T.; Suzuki, T.; Wang, W. W.; Nagase, S.; Fujii, T.;
Angew. Chem. 2014, 126, 9723-9725; Angew. Chem. Int. Ed. 2014, 53,
9569-9571.
6. Morosaki, T.; Wang, W. W.; Nagase, S.; Fujii, T.; Chem. Eur. J. 2015, 21,
15404–15411. J. doi: 10.1002/chem.201502166.
7. Fujii, T.; Suzuki, T.; Sato, T.; Horn, E.; Yoshimura, T.; Tetrahedron Lett.
2001, 42, 6151-6154.
8. (a) Sheldrick, G. M.; SHELXL-97, Program for crystal-structure
refinement, University of Göttingen, Göttingen (Germany), 1997;
(b) Sheldrick, G. M.; Acta Crystallogr. Sect. A 2008, 64, 112-
122.
Compound 2
To a mixture of 1 (12.8 mg, 30 μmol) and Ph3PAuCl (29.7 mg,
60 μmol) was added THF (2 mL) at −78°C. After stirring for
1 h, AgBF4 (11.7 mg, 60 μmol) was added. The resulting solu-
tion was stirred overnight. The reaction mixture was filtered
through Celite with DCM. Concentration of the filtrate under
reduced pressure afforded the desired product (46.5 mg, 95%).
The solid product of 2 suitable for X-ray analysis was recrystal-
lized in acetone/Et2O to yield colorless crystals.
2: 1H NMR (500 MHz, CDCl3) δ 2.61 (s, 3H), 2.89 (d, 2JPH
= 14.0 Hz, 3H), 6.94–6.98 (m, 12H), 7.26–7.31 (m, 12H), 7.35–
7.38 (m, 4H), 7.46–7.55 (m, 12H), 7.60–7.63 (m, 2H), 8.00–8.01
(m, 4H), 8.04–8.08 (m, 4H); 1H NMR (500 MHz, CD3CN) δ 2.67
(s, 3H), 2.82 (d, 2JPH = 12.5 Hz, 3H), 7.03–7.08 (m, 12H), 7.38–
7.43 (m, 16H), 7.48–7.51 (m, 4H), 7.58–7.61 (m, 6H), 7.65–7.70
(m, 4H), 8.02–8.09 (m, 8H); 31P NMR (202 MHz, CDCl3) δ
28.60, 34.98; 31P NMR (202 MHz, CD3CN) δ 28.73, 35.40.
Compound 2 crystallizes in the triclinic space group P–1
(No. 2), C 69 H 68 Au 2 B 2 F 8 N O 2 P 3 S, M = 1635.77 g mol−1
,
9. Guha, A. K.; Borthakur, B.; Phukan, A. K.; J. Org. Chem. 2015, 80,
7301-7304.
10. Alcarazo, M.; Radkowski, K.; Mehler, G.; Goddard, R.; Fürstner, A.;
Chem. Commun. 2013, 49, 3140-3142.
11. (a) Becke, A. D.; Phys. Rev. 1988, A 38, 3098-3100. (b) Becke, A. D.; J.
Chem. Phys. 1993, 98, 5648-5652. (c) Perdew, J. P.; Wang, Y.; Phys. Rev.
1996, B 45, 13244-13249.
˚
crystal dimensions 0.45 × 0.21 × 0.10 mm, a = 11.358(9) A,
3
˚
˚
˚
b = 11.767(1) A, c = 13.732(6) A, V = 1637.0(1) A , Z = 1,
θ
= 3.06°, θ
= 27.51°, ρ = 1.659 g·cm−1, μ (MoKα) =
min
max
4.649 mm−1, F000 = 806, –13 ࣘ h ࣘ 14, –15 ࣘ k ࣘ 15, –17 ࣘ l
ࣘ 17, 16022 reflections measured, 12127 unique (Rint = 0.0303),
R1 = 0.0272 (I > 2.0σ (I)), Rw = 0.728 (all data), GooF = 1,037,
787 parameters, 93 restraints.
12. (a) Gaussian 09, Revision B.01, Frisch, M. J.; Trucks, G. W.; Schlegel,
H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.;
Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.;
Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnen-
berg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.;
Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd,
J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi,
R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S.
S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.;
Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Strat-
mann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochter-
ski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G.
A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas,
O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.; Gaussian, Inc.
Wallingford CT, 2010. (b)NBO version 3.1, Glendening, E. D.; Reed,
A. E.; Carpenter, J. E.; Weinhold, F. (c) Reed, A. E.; Curtiss, L. A.; Wein-
hold, F.; Chem. Rev. 1988, 88, 899–926. (d) Reed, A. E.; Weinhold, F.;
J. Chem. Phys. 1985, 83, 1736–1740.
Funding
This work was partially supported by Grants-in-AID for Scientific
Research(c) (No.15K05438) from the Ministry of Education, Culture,
Sports, Science, and Technology of Japan and research fellow of the Japan
Society for the Promotion of Science for Young Scientists (No.15J05047).
References
1. (a) Tonner, R.; Öxler, F.; Neumüller, B.; Petz, W.; Frenking, G.; Angew.
Chem. 2006, 118, 8206-8211; Angew. Chem. Int. Ed. 2006, 45, 8038-
8042, (b) Tonner, R., Frenking, G.; Chem. Eur. J. 2008, 14, 3260-
3272, (c) Tonner, R.; Frenking, G.; Chem. Eur. J. 2008, 14, 3273-3289.
(d) Tonner, R.; Heydenrych, G.; Frenking, G.; Chem. Phys. Chem.
2008, 9, 1474-1481. (e) Frenking, G.; Tonner, R.; Pure Appl. Chem.
2009, 81, 597-614. (f) Petz, W.; Frenking, G.; Top. Organomet. Chem.
2010, 30, 49-92. (g) Takagi, N.; Tonner, R.; Frenking, G.; Chem. Eur. J.
2012, 18, 1772-1780. (h) Frenking, G.; Tonner, R.; Klein, S.; Takagi, N.;
13. Vicente, J.; Singhal, A. R.; Jones, P. G.; Organometallics 2002, 21, 5887-
5900.
14. Schmidbaur, H.; Schier, A.; Chem. Soc. Rev. 2012, 41, 370-412.