Organometallics
ARTICLE
Table 5. Selected Bond Lengths (Å) and Angles (deg) in
Complex 17
filtration, washed with Et2O, and dried under vacuum to afford complex 8as
a yellow solid (71%, 0.21 g). 31P{1H} NMR (162.0 MHz, CD2Cl2, 25 °C):
δ 50.2 ppm (s). 1H NMR (CDCl3, 400.1 MHz, 25 °C): δ 9.75 (d, J = 5.2
Hz, 1H), 7.74 (d, J = 5.4 Hz, 1H), 7.49ꢀ7.39 (m, 10H), 7.36ꢀ7.18 (m,
7H), 7.10ꢀ6.99 (m, 11H), 6.89ꢀ6.80 (m, 8H), 6.72ꢀ6.65 (m, 3H), 6.41
(d, J = 7.8 Hz, 1H), 4.80 (s, 1H; CdCHC(CH3)3), 4.70 (d, J = 13.1 Hz,
1H; ArCH2), 4.54 (d, J = 15.0 Hz, 1H; PyCH2), 4.07 (d, J = 13.2 Hz, 1H;
ArCH2), 3.68 (d, J = 16.7 Hz, 1H; PyCH2), 3.64 (d, J = 14.7 Hz, 1H;
PyCH2), 3.10 (d, J = 14.7 Hz, 1H; PyCH2), 1.29 (s, 9H; CtCC(CH3)3),
0.76 (s, 9H; C=CHC(CH3)3). 13C{1H} NMR (100.6 MHz, CDCl3,
25 °C): δ 164.9, 164.4, 163.9, 163.4, 155.7, 148.6, 144.7 (CtCCdCH),
141.2, 136.8, 136.4, 134.7, 133.6 (CdCHC(CH3)3), 132.7, 132.6, 130.9,
129.5, 129.3, 129.0, 128.7, 128.3, 128.1, 127.9, 127.6, 127.2, 125.7, 123.7
(CtCCdCH), 123.4, 122.0, 121.4, 70.5 (PyCH2), 67.8 (ArCH2), 64.8
(PyCH2), 48.9 (CtCCdCH), 35.3 (CdCHC(CH3)3), 33.7
(CtCC(CH3)3), 32.5 (CtCC(CH3)3), 29.7 (CdCHC(CH3)3). Anal.
Calcd for C67H69BN3OPRu: C, 74.85; H, 6.47; N, 3.91. Found: C, 74.99;
H, 6.19; N, 4.08. HRMS (MALDI, matrix CHCA): m/z calcd for
C43H47N3PRuþ 738.2546, found 738.4191 [M ꢀ BPh4]þ.
Bond Distances
Ru(1)ꢀN(10)
Ru(1)ꢀN(20)
Ru(1)-O(1A)
2.0650(16)
2.1019(17)
2.1681(13)
Ru(1)ꢀN(1)
Ru(1)ꢀO(1)
Ru(1)ꢀP(1)
2.0958(16)
2.1468(13)
2.2502(5)
Bond Angles
80.94(6) N(10)ꢀRu(1)ꢀN(20) 162.96(7)
N(10)ꢀRu(1)ꢀN(1)
N(1)ꢀRu(1)ꢀN(20)
N(1)ꢀRu(1)ꢀO(1)
N(10)ꢀRu(1)ꢀO(1A)
N(20)ꢀRu(1)ꢀO(1A)
N(10)ꢀRu(1)ꢀP(1)
N(20)ꢀRu(1)ꢀP(1)
O(1A)-Ru(1)ꢀP(1)
82.58(7) N(10)ꢀRu(1)ꢀO(1)
168.69(6) N(20)ꢀRu(1)ꢀO(1)
84.77(6) N(1)ꢀRu(1)ꢀO(1A)
91.02(6) O(1)ꢀRu(1)ꢀO(1A)
96.28(5) N(1)ꢀRu(1)ꢀP(1)
88.77(5) O(1)ꢀRu(1)ꢀP(1)
96.01(6)
99.33(6)
90.28(6)
78.58(6)
92.68(5)
98.49(4)
176.98(4) Ru(1)ꢀO(1)ꢀRu(1A) 101.42(6)
Complex 13. A mixture of complex 1 (0.10 g, 0.10 mmol), tert-
butylacetylene (7; 0.25 mL, 2.0 mmol), and H2O (0.2 mL) in THF
(8 mL) was stirred under N2 in a sealed tube at 90 °C for 6 h. The
reaction mixture was cooled to room temperature, and Na2SO4 was added.
After 2 h, the solid was removed by filtration, the filtrate was concentrated to
approximately 1 mL, and Et2O (7 mL) was added to give a white precipitate.
The solid was collected by filtration, washed with a mixed solvent of CH2Cl2
and Et2O (1:5), and dried under vacuum to afford complex 13 as a white
solid (76%, 76 mg). 31P{1H} NMR (162.0 MHz, CD2Cl2, 25 °C): δ 56.7
ppm (s). 1H NMR (400.1 MHz, (CD3)2CO, 25 °C): δ 8.81 (d, J = 5.5 Hz,
1H), 8.25 (d, J = 5.3 Hz, 1H), 7.76ꢀ7.68 (m, 2H), 7.64ꢀ7.42 (m, 9H),
7.39ꢀ7.35 (m, 8H), 7.29ꢀ7.21 (m, 3H), 7.19ꢀ7.14 (m, 4H), 7.02ꢀ6.98
(m, 2H), 6.93 (t, J = 7.4 Hz, 8H), 6.78 (t, J = 7.2 Hz, 4H), 5.07 (d, J = 14.1
Hz, 1H; ArCH2), 5.05 (d, J = 16.1 Hz; PyCH2), 4.73 (d, J = 17.2 Hz;
PyCH2), 4.45 (d, J = 16.1 Hz; PyCH2), 4.32 (dd, J1 = 14.1 Hz, J2 = 1.0 Hz,
1H; ArCH2), 4.23 (d, J = 17.2 Hz; PyCH2), 1.59 (t, J = 10.8 Hz, 1H;
RuCH2), 0.90 (d, J = 10.8 Hz, 1H; RuCH2), 0.54 (s, 9H; CH2C(CH3)3).
13C{1H} NMR (100.6 MHz, CD2Cl2, 25 °C): δ 207.0 (d, J = 18 Hz),
165.1, 164.7, 164.2, 163.7, 156.6, 156.0, 152.0, 150.2, 141.7, 141.5, 138.3,
137.8, 137.5, 136.4, 135.7, 135.2, 133.9, 133.7, 133.6, 133.0, 132.3, 131.9,
131.8, 130.6, 129.9, 129.6, 128.8, 128.7, 128.6, 128.5, 126.6, 126.2, 126.1,
124.8, 124.7, 122.9, 122.4, 121.7, 70.6 (PyCH2), 66.8 (PyCH2), 62.6 (d, J =
4 Hz, ArCH2), 37.3 (C(CH3)3), 33.6 (C(CH3)3 and RuCH2). Anal. Calcd
for C61H59BN3OPRu: C, 73.78; H, 5.99; N, 4.23. Found: C, 73.45; H, 6.02;
N, 4.09. HRMS (MALDI, matrix CHCA): m/z calcd for C37H39N3OPRuþ
674.1869, found 674.3293 [M ꢀ BPh4]þ.
calcium hydride (dichloromethane). [Ru(N3P)(OAc)](BPh4) (1) was
prepared according to the literature method.21 Other chemicals were
used as received from Aldrich. Elemental analyses were performed by M-H-
W Laboratories (Phoenix, AZ). Mass spectra were collected on a MALDI
Micro MX mass spectrometer (MALDI) and an API QSTAR XL System
(ESI). 1H, 13C{1H}, and 31P{1H} NMR spectra were collected on a Bruker
AV 400 MHz NMR spectrometer. 2D NMR spectra were collected on a
JEOL EX 400 MHz NMR spectrometer. 1H and 13C{1H} NMR chemical
shifts are relative to TMS or the residue of deuterium solvents, and 31P{1H}
NMR chemical shifts are relative to 85% H3PO4.
Complex 4. A mixture of [Ru(N3P)(OAc)](BPh4) (1; 0.15 g,
0.16 mmol), 3-butyn-1-ol (2; 60 μL, 0.76 mmol), and DIPEA (130 μL,
0.76 mmol) in THF (5 mL) was stirred under N2 at 80 °C for 1 h. The
mixture was cooled to room temperature and concentrated to approxi-
mately 3 mL. The precipitated solid was collected by filtration, washed
with THF, Et2O, and hexane, and dried under vacuum to afford complex
4 as a yellow solid (68%, 0.11 g). 31P{1H} NMR (162.0 MHz, CD2Cl2,
1
25 °C): δ 53.4 ppm (s). H NMR (400.1 MHz, CD2Cl2, 25 °C): δ
8.72ꢀ8.70 (m, 1H), 8.38 (d, J = 4.8 Hz, 1H), 7.70ꢀ7.66 (m, 2H),
7.63ꢀ7.57 (m, 2H), 7.44ꢀ7.34 (m, 14H), 7.29ꢀ7.17 (m, 3H), 7.06ꢀ6.99
(m, 12H), 6.87 (t, J = 7.2 Hz, 4H), 6.78ꢀ6.74 (m, 2H), 6.57 (d, J = 7.8 Hz,
1H), 4.64 (d, J = 13.0 Hz, 1H; ArCH2), 4.25 (q, J1 = 16.4, J2 = 8.7 Hz;
RudC(Oꢀ)CH2CH2CH2ꢀ), 4.06 (d, J = 17.4 Hz, 1H; PyCH2),
4.01ꢀ3.95 (m, 1H; RudC(Oꢀ)CH2CH2CH2ꢀ), 3.76 (d, J = 13.2 Hz,
1H; ArCH2), 3.72ꢀ3.65 (m, 1H; RudC(Oꢀ)CH2), 3.40 (d, J = 15.4 Hz,
1H; PyCH2), 3.22 (d, J = 15.4 Hz, 1H; PyCH2), 3.06 (d, J = 17.4 Hz, 1H;
PyCH2), 2.04ꢀ1.92 (m, 1H; RudC(Oꢀ)CH2), 1.97 (s, 3H; COCH3),
1.90ꢀ1.81 (m, 1H; RudC(Oꢀ)CH2CH2), 1.75ꢀ1.66 (m, 1H; RudC-
(Oꢀ)CH2CH2). 13C{1H} NMR (CD2Cl2, 100.6 MHz, 25 °C): δ 312.7
(d, J = 14 Hz, RudC), 177.2 (CH3CO), 165.4, 157.4, 156.6, 149.0, 138.4,
137.8, 136.4, 135.8, 134.5, 134.4, 132.6, 132.5, 132.1, 129.9, 129.4, 128.2,
128.1, 127.9, 127.7, 126.1, 122.3, 120.1, 81.7 (RudC(Oꢀ)CH2CH2-
CH2ꢀ), 74.2 (PyCH2), 67.7 (d, J = 4 Hz, ArCH2), 65.9 (PyCH2), 53.2
(RudC(Oꢀ)CH2CH2CH2ꢀ), 25.1 (CH3CO), 22.5 (RudC(Oꢀ)CH2-
[D2] Complex 16. A mixture of complex 1 (0.10 g, 0.10 mmol), tert-
butylacetylene (7; 0.25 mL, 2.0 mmol) and D2O (0.2 mL) in THF
(8 mL) was stirred under N2 in a sealed tube at 90 °C for 6 h. The
reaction mixture was cooled to room temperature, and Na2SO4 was added.
After 2 h, the solid was removed by filtration, the filtrate was concentrated to
approximately 1 mL, and Et2O (7 mL) was added to give a white precipitate.
The solid was collected by filtration, washed with a mixed solvent of CH2Cl2
and Et2O (1:5), and dried under vacuum to afford complex 18 as a white
solid (68%, 68 mg). 31P{1H} NMR (162.0 MHz, CD2Cl2, 25 °C): δ 56.8
ppm (s). 1H NMR (400.1 MHz, (CD3)2CO, 25 °C): δ 8.82 (d, J = 5.6 Hz,
1H), 8.26 (d, J = 5.2 Hz, 1H), 7.78ꢀ7.68 (m, 2H), 7.66ꢀ7.46 (m, 9H),
7.38ꢀ7.34 (m, 8H), 7.29ꢀ7.23 (m, 3H), 7.19ꢀ7.14 (m, 4H), 7.06ꢀ6.70
(m, 2H), 6.93 (t, J = 7.4 Hz, 8H), 6.78 (t, J = 7.2 Hz, 4H), 5.08 (d, J = 14.5
Hz, 2H; ArCH2 and PyCH2), 4.76 (d, J = 17.0 Hz, 1H; PyCH2), 4.50 (d, J =
16.1 Hz; PyCH2), 4.35 (dd, J1 = 14.2 Hz, J2 = 1.2 Hz, 1H; ArCH2), 4.27 (d,
J = 17.2 Hz; PyCH2), 0.53 (s, 9H; CH2C(CH3)3). 2D NMR (61.3 MHz,
(CH3)2CO (set as δ 2.20 ppm), 25 °C): δ 1.66 (1D; RuCD2); 0.99
ppm (1D; RuCD2). Anal. Calcd for C61H57D2BN3OPRu: C, 73.63; HþD,
6.18; N, 4.22. Found: C, 73.75; H, 5.84; N, 4.26. HRMS (MALDI, matrix
CH2CH2ꢀ) ppm. Anal. Calcd for C61H57BN3O3PRu 0.5(hexane): C,
3
72.10; H, 6.05; N, 3.94. Found: C, 72.64; H, 5.94; N, 3.97. HRMS (ESI): m/
z calcd for C37H37N3O3PRuþ 704.1611, found 704.1570 [M ꢀ BPh4]þ.
Complex 8. A mixture of complex 1 (0.3 g, 0.3 mmol) and tert-
butylacetylene (7; 0.38 mL, 3.0 mmol) in THF (12 mL) was stirred under
N2 in a sealed tube at 90 °C for 20 min. The reaction mixture was cooled to
room temperature, and the solution was concentrated to 1 mL; then Et2O
(10 mL) was added to give a precipitate. The solvent was removed by filtra-
tion, and the solid was dissolved in CH2Cl2 (1mL);thenEt2O(10mL) was
added to the solution to afford a precipitate. The solid was collected by
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dx.doi.org/10.1021/om2001684 |Organometallics 2011, 30, 2571–2580