8
A.V. Smarun et al. / Journal of Organometallic Chemistry 834 (2017) 1e9
(sl br s, NCCH3), 120.2 (s, Im-CH), 93.6 (br s, Cp-CCH3), 75.2 (br s, Cp-
CH), 70.3 (br s, Cp-CH), 36.1 (d, J ¼ 8.0, NCH3) 35.2 (s, NCC(CH3)3),
31.2 (s, PC(CH3)3), 30.2 (s, PC(CH3)3), 12.3 (s, Cp-CH3), 2.8 ppm (s,
NCCH3). Note: several resonance signals related to carbon atoms in
tert-butyl moieties are not listed due to overlapping with solvent
peak at 29.8 ppm. 31P{1H} NMR (202.38 MHz, acetone-d6)
3.5.6. [6f][PF6]
1.66 mL (0.28 mmol) of tBu2P-Im and 110 mg (0.23 mmol) of [4f]
[PF6]. Yield: 123 mg (79%, dark-green powder). 1H NMR (500 MHz,
acetone-d6)
NCH3), 2.55 (s, 3H, NCCH3), 1.68 (s, 6H, Cp-CH3),1.66 (s, 3H, Cp-CH3),
1.53 (s, 9H, P-tBu), 1.50 (s, 9H, P-tBu), 1.47 ppm (s, 9H, Im-tBu). 13
{1H} NMR (125.7 MHz, acetone-d6)
d 7.11 (s, 1H, Im-CH), 4.47 (s, 2H, Cp-CH), 3.88 (s, 3H,
C
d
58.8 ppm. Anal. Calcd for C24H41F6N3P2Ru: C, 44.44; H, 6.37; N,
d
152.7 (d, J ¼ 14.5, CC4H9), 149.1
6.48. Found: C, 44.31; H, 6.32; N, 6.49. HRMS: m/z (M-CH3CN)þ
¼
(d, J ¼ 19.7, NCP), 127.5 (s, NCCH3), 120.8 (s, Im-CH), 87.6 (s, Cp-
CCH3), 82.1 (s, Cp-CCH3), 72.8 (s, Cp-CH), 35.9 (d, J ¼ 6.8, NCH3), 35.4
(s, NCC(CH3)3), 31.5 (s, PC(CH3)3), 30.2 (s, PC(CH3)3), 12.3 (s, Cp-
CH3), 11.5 (s, Cp-CH3), 3.1 ppm (s, NCCH3). Note: several resonance
signals related to carbon atoms in tert-butyl moieties are not listed
due to overlapping with solvent peak at 29.8 ppm. 31P{1H} NMR
(Calculated for RuC22H38N2P, 463.1816) found 463.1833.
3.5.3. [6c][PF6]
1.71 mL (0.29 mmol) of tBu2P-Im and 110 mg (0.24 mmol) of [4c]
[PF6]. Yield: 125 mg (79%, yellow-brown powder). 1H NMR
(202.38 MHz, acetone-d6)
d
56.8 ppm. Anal. Calcd for
(500 MHz, acetone-d6)
d 7.06 (s, 1H, Im-CH), 4.66 (v br s, 2H, Cp-
C
26H45F6N3P2Ru: C, 46.15; H, 6.70; N, 6.21. Found: C, 46.06; H, 6.74;
CH), 4.08 (t, J ¼ 2.1 Hz, 1H, Cp-CH), 3.87 (s, 3H, NCH3), 2.58 (s, 3H,
NCCH3), 1.76 (br s, 6H, Cp-CH3), 1.49 (br s, 9H, P-tBu), 1.47 (br s, 9H,
P-tBu), 1.40 ppm (s, 9H, Im-tBu). Note: resonance signal of cyclo-
pentadienyl proton at 4.66 ppm is barely visible presumably due to
N, 6.21. HRMS: m/z (M-CH3CN)þ ¼ (Calculated for RuC24H42N2P,
491.2129) found 491.2138.
coalescence. 13C{1H} NMR (125.7 MHz, acetone-d6)
d 152.4 (d,
3.5.7. [6g][PF6]
1.61 mL (0.27 mmol) of tBu2P-Im and 110 mg (0.22 mmol) of [4g]
J ¼ 12.9, CC4H9), 149.4 (d, J ¼ 20.8, NCP), 127.2 (sl br s, NCCH3), 120.1
(s, Im-CH), 96.0 (br s, Cp-CCH3), 75.0 (br s, Cp-CH), 72.3 (br s, Cp-
CH), 36.4 (br s, NCH3), 35.3 (s, NCC(CH3)3), 31.2 (s, PC(CH3)3), 10.9 (s,
Cp-CH3), 3.0 ppm (s, NCCH3). Note: several resonance signals
related to carbon atoms in tert-butyl moieties are not listed due to
overlapping with solvent peak at 29.8 ppm. 31P{1H} NMR
[PF6]. Yield: 139 mg (90%, dark-brown powder). 1H NMR (500 MHz,
acetone-d6)
d 7.10 (s, 1H, Im-CH), 4.24 (s, 1H, Cp-CH), 3.88 (s, 3H,
NCH3), 2.53 (s, 3H, NCCH3), 1.80 (br s, 6H, Cp-CH3), 1.65 (s, 6H, Cp-
CH3), 1.53 (s, 9H, P-tBu), 1.50 (s, 9H, P-tBu), 1.45 ppm (s, 9H, Im-tBu).
13C{1H} NMR (125.7 MHz, acetone-d6)
d
152.8 (d, J ¼ 13.8, CC4H9),
149.2 (d, J ¼ 20.3, NCP), 127.4 (s, NCCH3), 120.7 (s, Im-CH), 87.2 (s,
Cp-CCH3), 70.1 (s, Cp-CH), 36.1 (d, J ¼ 8.0, NCH3), 35.6 (s,
NCC(CH3)3), 31.3 (s, PC(CH3)3), 30.2 (s, PC(CH3)3), 12.0 (s, Cp-CH3),
9.8 (s, Cp-CH3), 3.0 ppm (s, NCCH3). Note: several resonance signals
related to carbon atoms in tert-butyl moieties are not listed due to
overlapping with solvent peak at 29.8 ppm. 31P{1H} NMR
(202.38 MHz, acetone-d6)
d
59.0 ppm. Anal. Calcd for
C
25H43F6N3P2Ru: C, 45.31; H, 6.54; N, 6.34. Found: C, 45.25; H, 6.48;
N, 6.36. HRMS: m/z (M-CH3CN)þ ¼ (Calculated for RuC23H40N2P,
477.1973) found 477.1976.
3.5.4. [6d][PF6]
(202.38 MHz, acetone-d6)
d 54.72 ppm. Anal. Calcd for
1.71 mL (0.29 mmol) of tBu2P-Im and 110 mg (0.24 mmol) of [4d]
C
27H47F6N3P2Ru: C, 46.95; H, 6.86; N, 6.08. Found: C, 46.97; H, 6.87;
[PF6]. Yield: 123 mg (78%, yellow-brown powder). 1H NMR
N, 6.10. HRMS: m/z (M-CH3CN)þ ¼ (Calculated for RuC25H44N2P,
(500 MHz, acetone-d6) d 7.11 (s, 1H, Im-CH), 4.57 (s, 1H, Cp-CH), 4.14
505.2286) found 505.2295.
(br s, 2H, Cp-CH), 3.90 (s, 3H, NCH3), 2.52 (s, 3H, NCCH3), 1.75 (s, 6H,
Cp-CH3), 1.53 (s, 9H, P-tBu), 1.50 (s, 9H, P-tBu), 1.37 ppm (s, 9H,
3.5.8. [8][PF6]/[9][PF6]
Im-tBu). 13C{1H} NMR (125.7 MHz, acetone-d6)
d
152.8 (d, J ¼ 13.4,
Mixture of compounds 8þ and 9þ was obtained following the
modified procedure as for the synthesis of complexes 6þ. Ligand 7
(4.56 mL, 0.055 M, 0.25 mmol) was reacted with 105 mg
(0.21 mmol) of [4h][PF6]. Yield: 109 mg (76%, dark-brown powder).
CC4H9), 149.2 (d, J ¼ 20.2, NCP), 127.3 (sl br s, NCCH3), 120.6 (s, Im-
CH), 72.6 (s, Cp-CH), 72.6 (s, Cp-CH), 35.7 (d, J ¼ 9.0, NCH3), 35.7 (s,
NCC(CH3)3), 31.4 (s, PC(CH3)3), 30.2 (s, PC(CH3)3), 12.8 (s, Cp-CH3),
2.9 ppm (s, NCCH3). Note: several resonance signals related to
carbon atoms in tert-butyl moieties are not listed due to over-
lapping with solvent peak at 29.8 ppm. 31P{1H} NMR (202.38 MHz,
31P{1H} NMR (202.38 MHz, acetone-d6)
d 40.7 ppm.
3.6. General procedure for isomerization of 1-hexene
acetone-d6)
d 58.0 ppm. Anal. Calcd for C25H43F6N3P2Ru: C, 45.31;
H, 6.54; N, 6.34. Found: C, 45.24; H, 6.47; N, 6.37. HRMS: m/z (M-
In a typical reaction of 1-hexene isomerization, 2 mol% of
complex [6][PF6] was transferred into a J Young NMR tube. The
complex was dissolved in 0.80 mL of acetone-d6 followed by
0.05 mL (0.4 mmol) of 1-hexene. After the tube was sealed all its
contents were thoroughly mixed together and the tube was heated
to 60 ꢀC in using an oil bath. The reaction progress was followed by
1H NMR spectroscopy.
CH3CN)þ ¼ (Calculated for RuC23H40N2P, 477.1973) found 477.1979.
3.5.5. [6e][PF6]
1.66 mL (0.28 mmol) of tBu2P-Im and 110 mg (0.23 mmol) of [4e]
[PF6]. Yield: 128 mg (82%, yellow-brown powder). 1H NMR
(400 MHz, acetone-d6)
d 7.01 (s, 1H, Im-CH), 4.19 (s, 2H, Cp-CH),
3.85 (s, 3H, NCH3), 2.52 (s, 3H, NCCH3), 1.78 (br s, 6H, Cp-CH3), 1.71
(s, 3H, Cp-CH3), 1.48 (s, 9H, P-tBu), 1.44 (s, 9H, P-tBu), 1.35 ppm (s,
Author information
9H, Im-tBu). 13C{1H} NMR (125.7 MHz, acetone-d6)
d 152.6 (d,
J ¼ 13.4, CC4H9), 149.2 (d, J ¼ 21.4, NCP), 127.1 (s, NCCH3), 120.6 (s,
Im-CH), 87.6 (s, Cp-CCH3), 67.2 (s, Cp-CH), 36.5 (s, NCH3), 35.5 (s,
NCC(CH3)3), 31.1 (s, PC(CH3)3), 30.2 (s, PC(CH3)3), 12.0 (s, Cp-CH3),
8.6 (s, Cp-CH3), 3.0 ppm (s, NCCH3). Note: several resonance signals
related to carbon atoms in tert-butyl moieties are not listed due to
overlapping with solvent peak at 29.8 ppm. 31P{1H} NMR
The authors declare no competing financial interests.
Acknowledgment
We thank Nanyang Technological University (Tier 1, M4011667)
for financial support.
(202.38 MHz, acetone-d6)
d
58.0 ppm. Anal. Calcd for
C
26H45F6N3P2Ru: C, 46.15; H, 6.70; N, 6.21. Found: C, 46.05; H, 6.77;
Appendix A. Supplementary data
N, 6.23. HRMS: m/z (M-CH3CN)þ ¼ (Calculated for RuC24H42N2P,
491.2129) found 491.2151.
Supplementary data related to this article can be found at http://