Article
Organometallics, Vol. 29, No. 6, 2010 1419
(d, 1H, J 6, Cy), 5.92 (d, 2H, J 6, Cy), 6.07 (d, 1H, J 6, Cy), 7.08
(dt, 1H, J 7.5, 1, H4), 7.29 (dt, 1H, J 7.5, 1.5 H5), 7.40 (dd, 1H,
J 7.5, 1, H3), 8.03 (d, 1H, J 7.5, H6). 13C NMR: δ 3.54 (NCMe),
18.97 (Cy-MeC6H4), 21.35, 23.54 (Cy-CHMeMe0), 27.65, 28.04
(oxaz-MeMe0) 31.28 (CyCHMeMe), 67.28 (iCMe2), 81.55,
82.24, 91.35, 91.37, (CH (C6H4Cy)), 81.95 (CH2), 104.64,
105.92 (C (C6H4 Cy)), 124.03 (NCMe), 123.83, 126.99, 131.92,
139.72 (C3, C4, C5, C6), 173.12 (NCO), 175.92 (C1Ru). MS
(FAB): m/z (%) 410 [M]þ, 451 [M - NCMe]þ. IR: ν(CdN)
81.65 (OCH2), 91.93 (C5Me5), 124.56 (NCMe), 126.67, 127.05,
128.22, 129.96 131.92, 132.52, 133.61 (Ar-H), 142.64 (C8),
144.69 (C1), 168.71 (CNO) (other quaternary carbons are
not seen). MS (FAB): m/z 676 [M - NCMe]þ. IR: ν(CdN):
1624 cm-1; ν(CdO) 1695 cm-1
.
Preparation of 5a. Phenylacetylene (11 mg, 0.11 mmol) was
added to solution of 2a (73 mg, 0.11 mmol) in dichloromethane,
and the mixture was stirred for 1 h. The mixture was then filtered
through Celite to remove excess KPF6, and the filtrate was
evaporated to dryness and washed with hexane to give 5a as a
pale yellow solid (72 mg, 86%). Anal. Calcd for C31H36Ir-
N2OPF6: C, 47.14, H, 4.59, N, 3.55. Found: C, 47.28, H, 4.37,
1622 cm-1
.
Preparation of 3a. PhCtCPh (67 mg, 0.38 mmol) and KPF6
(103 mg, 0.56 mmol) were added to a solution of 1a (100 mg,
0.19 mmol) in acetonitrile; after stirring for 72 h, no insertion
was observed by ESMS. Other experiments (see above) show
that at this stage 2a was formed. The acetonitrile was replaced by
dichloromethane, and the solution was stirred for 24 h and
filtered through Celite to remove excess KPF6. The filtrate was
evaporated to dryness and then washed with hexane to give 3a as
a yellow solid (122 mg, 76%). Anal. Calcd for C37H40IrN2OPF6:
C, 51.32; H, 4.66; N, 3.24. Found: C, 51.12; H, 4.53; N, 3.31. 1H
NMR: δ 1.31 (s, 3H, CMeMe0), 1.37 (s, 3H, CMeMe0), 1.41 (s,
15H, Cp*), 2.00 (s, 3H, NCMe), 4.27 (d, 1H, J 9, OCHH0), 4.58
(d, 1H, J 9, OCHH0), 6.30 (br, 1H, Ph), 6.74 (br m, 2H, Ph), 6.81
(br m, 2H, Ph), 6.99 (m, 5H, H6, Ph), 7.24 (m, 2H, H4, Ph), 7.31
(dt, 1H, J 7.5, 1.5, H5), 7.72 (dd, 1H J 7.5, 1, H3). 13C NMR: δ
2.35 (NCMe), 8.74 (C5Me5), 24.64, 27.57 (2ꢀMe), 72.31
(CMeMe0), 81.50 (CH2), 91.66 (C5Me5), 124.80 (NCMe),
124.17, 125.32, 125.95, 127.52, 128.12, 131.72 132.40, 134.14
(Ar-H), 141.88 (C2), 146.3, 147.91 (C1, C7), 151.38 (iC, Ph of
alkyne), 152.40 (C8), 169.16 (CNO). MS (FAB): m/z 679 [M -
1
N, 3.47. H NMR: δ 1.14 (s, 3H, CMeMe0), 1.29 (s, 3H,
CMeMe0), 1.34 (s, 15H, Cp*), 1.99 (s, 3H, NCMe), 4.11 (d,
1H, J 9, OCHH0), 4.42 (d, 1H, J 9, OCHH0), 6.97 (m, 2H, Ph),
7.06 (m, 2H, H7, Ph), 7.20 (m, 4H, H4, H6, Ph), 7.41 (dt, 1H, J
7.5, 1.5, H5), 7.63 (dt, 1H, J 8, 1.5, H3). 13C NMR: δ 2.67
(NCMe), 8.93 (C5Me5), 24.89, 27.33 (2ꢀMe), 72.66 (CMeMe0),
81.08 (CH2), 91.55 (C5Me5), 121.84 (NCMe), 122.97 (iC, Ph),
125.82, 127.02, 125.82, 132.07, 132.11, 133.02 (Ar-H), 132.11
(C7), 143.63 (C1), 152.59 (iC, Ph of alkyne), 155.68 (C8), 169.00
(CNO). MS (FAB): m/z 602 [M - NCMe]þ. IR: ν(CdN)
1527 cm-1
.
Preparation of 5b. PhCtCH (33 mg, 0.33 mmol) was added to
solution of 2b (194 mg, 0.33 mmol) in dichloromethane; after
stirring overnight, the mixture was filtered through Celite,
1
evaporated to dryness, and then washed with hexane. The H
NMR spectrum suggested the compound was not pure, so it was
washed through a short plug of silica (DCM/NCMe) to give 5b
as an orange solid (120 mg, 53%). Anal. Calcd for C31H35Ru-
N2OPF6: C, 53.37, H, 5.06, N, 4.02. Found: C, 53.47, H, 5.01, N,
3.95. 1H NMR: δ 1.00 (s, 3H, oxz Me), 1.18 (d, 1H, J 7,
CHMeMe0), 1.21 (d, 1H, J 7, CHMeMe0), 1.58 (s, 3H, oxz
Me), 1.85 (s, 3H, NCMe), 2.06 (s, 3H, Me-Cy), 2.71 (sept, 1H,
J 7, CHMeM0), 4.32 (d, 1H, J 9, OCHH0), 4.35 (d, 1H, J 9,
OCHH0), 4.39 (dd, 1H, J 6, 1, Cy), 5.03 (dd, 1H, J 6, 1, Cy), 5.35
(dd, 1H, J 6, 1, Cy), 5.41 (dd, 1H, J 6, 1, Cy), 7.12 (m, 4H, H7,
Ph), 7.29 (m, 4H, H4, H6, Ph), 7.50 (dt, 1H, J 7.5, 1.5, H5), 7.68
(d, 1H, J 7.5, H3). 13C NMR: δ 3.05 (NCMe), 19.43 (Me-Cy),
22.73, 23.69 (CHMeMe0), 25.28, 27.63 (2ꢀMe), 31.37 (CH(iPr)),
71.01 (CMe2), 80.58 (CH2), 82.00, 84.76, 87.84, 88.68
(CH(C6H4)), 108.07, 113.97 (C(C6H4), 124.01 (NCMe),
125.60, 125.90, 127.28, 128.05, 130.66 131.43, 132.08 (Ar-H),
132.32 (C7), 143.72 (C1), 152.48 (iC, Ph of alkyne), 168.57
(CNO), 176.01 (C8). MS (FAB): m/z 512 [M - NCMe]þ. IR:
NCMe]þ. IR: ν(CdN) 1624 cm-1
.
Preparation of 3b. PhCtCPh (33 mg, 0.19 mmol) was added
to solution of 2b (100 mg, 0.17 mmol) in dichloromethane. After
stirring for 24 h the solution was evaporated to dryness and then
washed with hexane. The 1H NMR spectrum suggested the
compound was not pure, so it was washed through a short plug
of silica (DCM/NCMe) to give 3b as a pure complex as a green
solid (66 mg, 51%). Anal. Calcd for C37H39RuN2OPF6: C,
1
57.43, H, 5.08, N, 3.62. Found: C, 55.81, H, 4.67, N, 3.29. H
NMR: δ 1.09 (s, 3H, oxz Me), 1.11 (d, 1H, J 7, CHMeMe0), 1.31
(d, 1H, J 7, CHMeMe0), 1.59 (s, 3H, oxz Me), 1.78 (s, 3H,
NCMe), 2.27 (s, 3H, Me-Cy), 2.90 (sept, 1H, J 7, CHMeMe0),
4.34 (d, 1H, J 9, OCHH0), 4.35 (d, 1H, J 6, Cy), 4.47 (d, 1H, J 9,
OCHH0), 4.54 (d, 1H, J 6, Cy), 5.10 (d, 1H, J 6, Cy), 5.65 (d, 1H,
J 6, Cy), 6.18 (d, 1H, J 8, Ph), 6.73 (t, 1H, J 7.5, Ph), 6.83 (m, 3H,
Ph), 6.96 (m, 3H, Ph), 7.14 (d, 1H, J 7.5, H6), 7.31 (m, 3H, H4,
ν(CdN) 1635 cm-1
.
Ph), 7.38 (dt, 1H, J 7.5, 1.5, H5), 7.62 (dd, 1H, J 7.5, 1, H3). 13
NMR: 2.99 (NCMe), 19.57 (Me-Cy), 22.74, 24.45
C
Preparation of 6a. EtO2CCtCH (21 mg, 0.22 mmol) was
added to solution of 2a (75 mg, 0.11 mmol) in dichloromethane.
After stirring for 3 h, the mixture was filtered through Celite,
evaporated to dryness, and then washed with hexane to give 6a
as a pale yellow solid (70 mg, 82%). Anal. Calcd for C28H36Ir-
N2O3PF6: C, 42.80, H, 4.62, N, 3.57. Found: C, 42.70, H, 4.51,
δ
(CHMeMe0), 25.44, 28.28 (2ꢀMe), 31.61 CH(iPr)), 71.08
(CMe2), 81.57 (OCH2), 80.32, 85.32, 88.09, 91.28 (CH(C6H4)),
109.46, 112.61 (C(C6H4), 126.46 (NCMe), 124.32, 125.57,
126.25, 127.80, 128.49, 131.80 132.02, 133.58, (Ar-H),141.87
(C2), 145.92, 148.88 (C1, C7), 151.54 (iC, Ph of alkyne), 168.64
(C9), 171.46 (C8). MS (FAB): m/z 588 [M - NCMe]þ. IR:
1
N, 3.56. H NMR: δ 1.22 (s, 3H, CMeMe0), 1.27 (m, 3H,
ꢀ
CO2CH2CH3), 1.30 (s, 15H, Cp*), 1.37 (s, 3H, CMeMe), 2.71
ν(CdN) 1602 cm-1
.
(s, 3H, NCMe), 4.11 (m, 3H, CO2CH2CH3, overlap, d, 1H, J 9,
OCHH0), 4.38 (d, 1H, J 9, OCHH0), 7.22 (m, 2H, H4, H6), 7.45
(dt, 1H, J 7.5, 1.5, H5), 7.48 (s, 1H, H7), 7.62 (d, 1H, J 7.5, H3).
13C NMR: δ 3.93 (NCMe), 8.61 (C5Me5), 14.84 (CO2CH2CH3),
24.81, 27.37 (2ꢀMe), 60.52 (CO2CH2CH3), 72.99 (CMeMe0),
81.14 (OCH2), 91.67 (C5Me5), 123.25 (NCMe), 126.95, 131.82,
132.43, 133.09 (C3, C4, C5, C6), 136.60 (C7), 141.65, 144.01 (C1,
C8), 168.64 (CNO), 174.70 (CO2). MS (FAB): m/z 600 [M -
Preparation of 4a. PhCtCCO2Et (21 mg, 0.12 mmol) was
added to solution of 2a (75 mg, 0.11 mmol) in dichloromethane;
after stirring for 3 h, the solution was filtered through Celite,
1
evaporated to dryness, and then washed with hexane. The H
NMR spectrum suggested the compound was not pure, so it was
washed through a short plug of silica (DCM/NCMe) to give 4a
as a beige solid (66 mg, 51%). Anal. Calcd for C34H40Ir-
N2O3PF6: C, 47.38, H, 4.68, N, 3.25. Found: C, 47.25, H,
4.63, N, 3.16. 1H NMR: δ 1.31 (s, 3H, CMeMe0), 1.38 (m, 3H,
CO2CH2CH3), 1.41 (s, 15H, Cp*), 1.46 (s, 3H, CMeMe0), 2.77 (s,
3H, NCMe), 3.79 (m, 2H, CO2CH2CH3), 4.23 (d, 1H, J 9,
OCHH0), 4.53 (d, 1H, J 9, OCHH0), 7.06 (m, 3H, Ph), 7.26 (m,
NCMe]þ. IR: ν(CdN) 1622 cm-1; ν(CdO) 1682 cm-1
.
Preparation of 7a. PhCtCH (21.6 mg, 0.22 mmol) was added
to solution of 2a (73 mg, 0.11 mmol) in dichloromethane; after
stirring for 2 h, the mixture was filtered through Celite, evapo-
rated to dryness, and then washed with hexane to give 7a as a
brown solid (80 mg, 89%). Anal. Calcd for C37H39IrNOPF6: C,
2H, H4, H6, Ph), 7.36 (m, 1H, H5), 7.68 (dd, 1H, J 7.5, 1, H3). 13
C
1
NMR: δ 4.12 (NCMe), 8.53 (C5Me5), 14.15 (CO2CH2CH3),
52.23, H, 4.62, N, 1.65. Found: C, 52.23, H, 4.54, N, 1.64. H
NMR: δ 1.18 (s, 3H, CMeMe0), 1.37 (s, 3H, CMeMe0), 1.76
24.63, 27.24 (2xMe), 59.48 (CO2CH2CH3), 72.79 (CMeMe0),