Organometallics
Article
ppm, CDCl3): 8.00 (s, 2 H, N+CHCHN), 7.55 (s, 2H, N+CHCHN),
7.47 (s, 12 H, HAr), 7.34−7.33 (m, 8 H, HAr), 4.23 (m, 4 H,
NCH2CH2CH2CH2N), 3.48 (s, 6 H, N+CH3), 1.52 (s, 4 H,
NCH2CH2CH2CH2N). 31P (δ, ppm, CD3COCD3): −27.1 (s, PPh2).
Ru(III)-L2 was obtained as a yellow solid (yield: 80%) by
complexation of commercial RuCl3·3H2O with L2 at room temper-
ature according to the procedures as described in our previous work.29
The sample suitable for X-ray diffraction analysis was obtained by
recrystallization from acetone/n-hexane. FT-IR (KBr): 3167 (m),
3045 (m), 2935 (m), 2871 (m), 1641 (m), 1569 (m), 1486 (s), 1440
(s), 1267 (s), 1227 (s), 1150 (s), 1029 (s), 745 (s), 698 (s). CHN-
elemental analysis (found, %): C, 45.32; H, 3.91; N, 5.71 (calcd: C,
45.47; H, 4.07; N, 5.63). The complexation of commercial RuCl3·
3H2O with L2′ could not isolate the stable complex, because Ru-blacks
were formed during the procedure of filtering and washing by PE and
diethyl ether during product purification. The complex Ru-L2′ is more
sensitive to air and moisture than Ru-L2.
X-ray Crystallography. Intensity data were collected at 296 K for
Ru(III)-L2 on a Bruker SMARTAPEX II diffractometer using graphite
monochromated Mo Kα radiation (λ = 0.71073 Å). Data reduction
included absorption corrections by the multiscan method. The
structures were solved by direct methods and refined by full matrix
least-squares using SHELXS-97,30 with all non-hydrogen atoms refined
anisotropically. Hydrogen atoms were added at their geometrically
ideal positions and refined isotropically. The crystal data and
refinement details of Ru(III)-L1 and Ru(III)-L2 were given in
Table 5.
General Procedures for Hydroformylation−Acetalization−
Hydrogenolysis of Olefin in Alcohol. In a typical experiment for
tandem hydroformylation−acetalization−hydrogenolysis, the commer-
cial RuCl3·3H2O (0.15 mmol) and the isolated L2 (0.03 mmol) were
added into methanol (3 mL, or the other alcohol) and 1-octene (5
mmol, or the other olefin) sequentially. The obtained mixture in a 50
mL Teflon-lined stainless steel autoclave was sealed and pressured by
syngas to 4.0 MPa. The reaction mixture was stirred vigorously at the
appointed temperature for some time. Upon completion, the autoclave
was cooled down to room temperature and depressurized carefully.
The reaction solution was analyzed by GC to determine the
conversions (n-dodecane as internal standard), and the product
selectivities (normalization method) calibrated by the authentic
samples, and the products were further identified by GC-Mass.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was financially supported by the National Natural
Science Foundation of China (Nos. 21673077 and 21473058)
and Science Foundation of Shanghai (15ZR1411900).
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information associated with this article can be
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Accession Codes
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