Organometallics
Article
solution of THF and diethyl ether at room temperature. Anal. Calcd
ASSOCIATED CONTENT
Supporting Information
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−
1
for C H FeN P Si (816.74 g mol ): C, 64.71; H, 6.42; N, 3.43.
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52
2
4
sı
*
Found: C, 64.98; H, 6.34; N, 3.01%. mp >198 °C dec. IR (Nujol,
−
1
1
KBr, cm ): 3054 (Ar−H), 1873 (Fe−H), 943 (PMe ). H NMR
3
(
300 MHz, C D , δ, ppm): −19.01 (tdd, J = 66, 24, 6 Hz, 1H, Fe-H),
.47 (d, 9H, PMe ), 1.06 (d, 9H, PMe ), 4.42 (m, 2H, PCHaHbN),
6
6
IR, H, 31P, and 13C NMR spectra of 4 and 6; H and
1
1
0
3
3
1
3
5
.11 (m, 2H, PCHa′Hb′N), 6.70−7.26 (m, 20H, C H ), 7.81 (s, 4H,
6
5
31
C H ). P NMR (121 MHz, C D , δ, ppm): 13.1 (m, 1P, PMe ),
of H determined by GC (PDF)
2
6
4
6
6
3
2
1.3 (m, 1P, PMe ), 110.0 (m, 2P, PPh ).
Synthesis of Iron Nitrogen Hydride 6. A solution of Bu-Li
3
2
n
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(
34.4 mmol, 13.78 mL) was added dropwise to a stirred solution of
i
preligand 5′ C H (NHCH P Pr ) (14.1 mmol, 5.1 g) in Et O (60
6
4
2
2
2
2
mL) at 0 °C. After it warmed to room temperature, the reaction
continued for 8 h. Dichlorophenylsilane (16.9 mmol, 3.0 mL) was
added to the stirred solution, and then the resultant suspension was
stirred for 3 d. The supernatant was filtrated, and volatiles were
removed under reduced pressure, leaving a sticky oil. The solubility of
ligand 5 was extremely good even in n-pentane, and no further
purification was achieved. A solution of ligand 5 (1 mmol, 0.472 g) in
toluene (35 mL) was mixed with a solution of Fe(PMe ) (1.1 mmol,
Corresponding Author
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Xiaoyan Li − School of Chemistry and Chemical Engineering,
Key Laboratory of Special Functional Aggregated Materials,
3
4
0
.396 g) in toluene (30 mL) at −78 °C and then returned to room
temperature gradually. After the solution was stirred for 12 h, the
reaction temperature was elevated to 60 °C. The reaction lasted 5 d,
and then the volatiles were removed under reduced pressure. The
residue was extracted with n-pentane and diethyl ether. Yellow crystals
of 6 were obtained at room temperature from its n-pentane solution.
Anal. Calcd for C H FeN P Si (632.61 g mol ): C, 55.06; H, 8.13;
N, 8.86. Found: C, 54.78; H, 8.34; N, 9.01%. mp >160 °C dec. IR
Authors
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1
Yajie Wang − School of Chemistry and Chemical Engineering,
Key Laboratory of Special Functional Aggregated Materials,
Ministry of Education, Shandong University, Jinan 250100,
People’s Republic of China
Hua Zhang − School of Chemistry and Chemical Engineering,
Key Laboratory of Special Functional Aggregated Materials,
Ministry of Education, Shandong University, Jinan 250100,
People’s Republic of China
Shangqing Xie − School of Chemistry and Chemical
Engineering, Key Laboratory of Special Functional Aggregated
Materials, Ministry of Education, Shandong University, Jinan
250100, People’s Republic of China
29
51
4 3
−
1
(
(
Nujol, KBr, cm ): 2925 (Ar−H), 2049 (NN), 1887 (Fe−H), 952
1
PMe ). H NMR (300 MHz, C D , δ, ppm): −20.64 (td, J = 60, 24
3
6
6
Hz, 1H, Fe-H), 0.78 (m, 6H, PCHCH CH ), 0.90 (m, 6H,
PCHCH CH ), 1.22 (m, 6H, PCHCH CH ), 1.33 (m, 6H,
PCHCH CH ), 1.17 (d, 9H, PMe ), 1.16 (d, 9H, PMe ), 1.74 (m,
4
3
3
3
3
3
3
3
3
3
3
H, PCHCH CH ), 3.48 (m, 2H, PCH N), 3.38 (m, 2H, PCH N),
3 3 2 2
3
1
6
.92−7.13 (m, 4H, C H ), 7.33−8.28 (m, 5H, C H ). P NMR (121
6
4
6
5
MHz, C D , δ, ppm): 1.8 (t, J = 30 Hz, 1P, PMe ), 21.3 (d, J = 30 Hz
2
1
6
6
3
i
13
P, P Pr ). C NMR (75 MHz, C D , δ, ppm): 17.69 (s, PCHCH ),
2 6 6 3
9.99 (s, PCHCH ), 20.40 (s, PCHCH ), 20.61 (t, J = 2.25 Hz,
3
3
PCHCH ), 21.81 (d, J = 18 Hz, PCH3), 28.20 (q, J = 6.25 Hz,
Hongjian Sun − School of Chemistry and Chemical Engineering,
Key Laboratory of Special Functional Aggregated Materials,
3
PCHCH ), 30.76 (t, J = 4.5 Hz, PCHCH ), 51.10 (dt, J = 9, 13.5 Hz,
3
3
NCH P), 110.59 (s, Ar), 117.86 (s, Ar), 126.91 (s, Ar), 134.73 (s,
2
Ar), 146. 58 (s, Ar), 147.91 (s, Ar), 148.00 (s, Ar).
General Procedure for the Dehydration of Amides to
Nitriles. A 25 mL dried Schlenk tube including hydride 4 (0.005−
Olaf Fuhr − Institut fu
Leopoldshafen 76344, Germany
Dieter Fenske − Institut fur Nanotechnologie und Karlsruher
Nano-Micro-Facility, Karlsruher Institut fur Technologie,
Eggenstein-Leopoldshafen 76344, Germany
̈
r Nanotechnologie und Karlsruher Nano-
0
.04 mmol) was added to primary amides (1.0 mmol). After the
̈
r Technologie, Eggenstein-
Schlenk tube was purged with nitrogen, hydrosilanes (1−3 mmol)
and anhydrous solvent (3 mL) were added, respectively. The mixture
was stirred at corresponding temperature for 24 h. The product was
̈
̈
24
purified on the basis of the literature.
X-ray Structure Determination. Single-crystal X-ray diffraction
data for the complexes were collected on a Stoe StadiVari (4) or
XtaLAB Synergy, Dualflex, HyPix (6) diffractometer equipped with a
Mo Kα radiation (λ = 0.710 73 Å) or Ga Kα radiation (λ = 1.341 43)
and a charge coupled device (CCD) area detector. The structures
were solved using the charge-flipping algorithm, as implemented in
Notes
The authors declare no competing financial interest.
29
the program SUPERFLIP, and refined by full-matrix least-squares
2
ACKNOWLEDGMENTS
techniques against F (SHELXL) through the OLEX interface. All
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non-hydrogen atoms were refined anisotropically, and all hydrogen
atoms except for those of the disordered solvent molecules were
placed using AFIX instructions. Appropriate restraints or constraints
supplementary crystallographic data for this paper. Additional
crystallographic information is available in the Supporting Informa-
tion.
This work was supported by NSF China (Nos. 21971151/
21572119) and the major basic research projects of natural
science foundation of Shandong province ZR2019ZD46.
REFERENCES
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(
1) (a) Morales-Morales, D., Jensen, C. G. M. The Chemistry of
Pincer Compounds; Elsevier Science, 2007. (b) Chase, P. A.; Koten, G.
V. The Pincer Ligand: Its Chemistry and Applications (Catalytic Science),
H
Organometallics XXXX, XXX, XXX−XXX