Organometallics
Article
883.1494. Anal. Calcd for C81H54BF27P3Rh: C, 55.69; H, 3.12. Found:
C, 55.63; H, 3.46.
Hz), 109.6 (d, J = 96.8 Hz), 92.2−91.7 (m), 40.2 (d, J = 5.7 Hz),
33.9−32.5 (m, allyl-C C C H), 31.4, 30.5, 29.1, 22.2, 13.9; 31P NMR
(202 MHz, CDCl3) δP 51.78 (ddd, 1JP−Rh = 192.9, 2JP−P = 30.5, 3JP−P
= 13.2 Hz), 38.60 (dd, 1JP−Rh = 185.8,2JP−P = 30.3 Hz), 6.56 (d, 3JP−P
= 12.2 Hz); HRMS (ESI-TOF) m/z [M]+ calcd for C63H57P3Rh
1009.2723; found 1009.2715. Anal. Calcd for C95H69BF24P3Rh: C,
60.91; H, 3.71. Found: C, 60.36; H, 3.44.
Compound 2d: Prepared from 1 (20 mg, 0.012 mmol) and 4-
fluorophenyl acetylene (4 μL, 0.036 mmol) following general
procedure 1; red solid (10 mg, 49%); 1H NMR (500 MHz,
CDCl3) δH 7.64 (s, 8H), 7.60−7.52 (m, 2H), 7.50−7.38 (m, 10H),
7.32−7.18 (m, 7H), 7.17−6.83 (m, 27H), 6.67 (t, J = 8.5 Hz, 2H),
6.38−6.32 (m, 1H), 6.25 (dd, J = 10.7, 7.9 Hz, 2H), 3.18 (t, J = 4.6
Compound 4b: Prepared from 1 (40 mg, 0.023 mmol) and
trimethylsilyl acetylene (3.2 μL, 0.023 mmol) following general
procedure 1; red solid (41 mg, 97%); 1H NMR (500 MHz, CDCl3) δ
7.72 (s, 8H), 7.67−7.57 (m, 3H), 7.59−7.49 (m, 4H), 7.49 (s, 4H),
7.47−7.25 (m, 8H), 7.25−7.15 (m, 4H), 7.12 (ddd, J = 13.3, 7.8, 1.4
Hz, 3H), 7.08−6.92 (m, 12H), 6.91 (dd, J = 10.6, 7.4 Hz, 5H), 6.88−
6.80 (m, 2H), 6.80−6.72 (m, 1H), 5.93 (dd, J = 8.2, 5.9 Hz, 1H), 3.60
(ddd, J = 10.0, 4.2, 1.6 Hz, 1H), −0.17 (s, 9H); 13C NMR (126 MHz,
CDCl3) δC 161.9 (q, J = 49.8 Hz), 150.5 (dd, J = 42.8, 6.3 Hz), 147.4
(d, J = 25.6 Hz), 146.9, 135.3 (d, J = 14.1 Hz), 135.0 (br s), 134.8−
128.2 (18C), 128.1, 127.6 (d, J = 8.4 Hz), 127.2 (dd, J = 74.6, 6.5
Hz), 125.7, 124.7 (q, J = 272.7 Hz), 121.9 (d, J = 96.6 Hz), 117.8−
117.5 (m), 109.6 (d, J = 95.3 Hz), 105.6 (d, J = 8.2 Hz), 93.6 (td, J =
17.4, 15.8, 7.7 Hz), 36.4−34.7 (m), −0.9; 31P NMR (202 MHz,
CDCl3) δP 48.60 (ddd, 1JP−Rh = 188.6, 2JP−P = 28.0, 3JP−P = 14.0 Hz),
35.03 (dd, 1JP−Rh = 187.8, 2JP−P = 27.9 Hz), 2.92 (d, 3JP−P = 13.4 Hz);
HRMS (ESI-TOF) m/z [M]+ calcd for C60H53P3RhSi 997.2184;
found 997.2184.
1
Hz, 1H); 13C NMR (126 MHz, CDCl3) δC 162.0 (d, J(C−F) =
1
249.4 Hz), 161.9 (q, J(13C,11B) = 49.8 Hz), 149.7 (dd, J = 44.6, 5.9
Hz), 145.6 (d, J = 25.2 Hz), 143.9 (m, allyl C-C-C-H), 136.7 (br s),
135.0, 134.4 (d, J = 2.9 Hz), 134.2, 134.0 (dd, J = 33.0, 7.2 Hz), 134.0
(d, J = 18.1 Hz), 133.8 (d, J = 27.8 Hz), 133.8 (d, J = 13.5 Hz), 132.2
(d, J = 11.0 Hz), 132.0−131.4 (m), 131.5 (d, J = 10.3 Hz), 130.9 (dd,
J = 17.7, 7.7 Hz), 130.7 (d, J = 2.3 Hz), 130.4 (d, J = 2.1 Hz), 130.0
(d, J = 12.1 Hz), 129.9 (d, J = 2.3 Hz), 129.4 (d, J = 12.9 Hz), 129.0
2
3
(qq, J(F,C) = 31.5, J(B,C) = 2.9 Hz), 129.0 (d, J = 6.3 Hz), 128.5
(d, J = 10.4 Hz), 128.4 (d, J = 9.8 Hz), 128.4 (d, J = 10.0 Hz), 128.0
(d, J = 8.6 Hz), 127.3 (d, J = 7.1 Hz), 126.0 (d, J = 12.2 Hz), 124.7
(q, 1J(C,F) = 272.6 Hz), 120.0 (d, J = 95.4 Hz), 117.6, 115.1 (d, J =
21.6 Hz), 111.0 (d, J = 96.6 Hz), 108.5 (d, J = 9.6 Hz), 92.2−91.7
(m), 35.8−34.5 (m, allyl-C-C-C-H); 19F NMR (377 MHz, CDCl3) δF
−62.43, −113.01; 31P NMR (202 MHz, CDCl3) δ 49.84 (ddd, 1JP−Rh
2
3
1
= 188.8, JP−P = 29.6, JP−P = 12.4 Hz), 36.29 (dd, JP−Rh = 184.5,
2JP−P = 29.6 Hz), 6.79 (d, JP−P = 11.9 Hz); HRMS (ESI-TOF) m/z
3
[M]+ calcd for C63H48FP3Rh 1019.2008; found 1019.1978. Anal.
Calcd for C95H60BF25P3Rh: C, 60.59; H, 3.21. Found: C, 60.47; H,
3.25.
Compound 4c: Prepared from 1 (100 mg, 0.058 mmol) and
methyl propiolate (15 μL, 0.058 mmol) following general procedure
1
1; red solid (99 mg, 93%); H NMR (500 MHz, CDCl3) δH 7.76−
7.69 (m, 11H), 7.61 (td, J = 7.8, 3.2 Hz, 2H), 7.58−7.49 (m, 8H),
7.44−7.40 (m, 1H), 7.39−7.30 (m, 6H), 7.28−7.14 (m, 10H), 7.08−
6.91 (m, 14H), 6.79−6.72 (m, 2H), 6.62 (dd, J = 8.1, 5.8 Hz, 1H),
4.02 (ddd, J = 6.0, 4.6, 1.1 Hz, 1H), 3.56 (s, 3H); 13C NMR (126
Compound 2e: Prepared from 1 (20 mg, 0.012 mmol) and 4-
methoxyphenyl acetylene (4.5 μL, 0.036 mmol) following general
1
procedure 1; red solid (18 mg, 82%); H NMR (500 MHz, CDCl3)
δH 7.99 (s, 8H), 7.94−7.79 (m, 7H), 7.78 (s, 4H), 7.68−7.43 (m,
17H), 7.40 (dt, J = 7.0, 2.8 Hz, 5H), 7.37−7.32 (m, 2H), 7.31−7.26
(m, 6H), 7.25 (s, 3H), 7.20 (t, J = 7.2 Hz, 2H), 6.88 (d, J = 8.3 Hz,
2H), 6.66 (ddd, J = 19.1, 9.5, 6.9 Hz, 3H), 4.01 (s, 3H), 3.61−3.51
1
MHz, CDCl3) δC 168.16−165.88 (m), 161.87 (q, J(13C,11B) = 49.9
Hz), 148.47 (dd, J = 46.0, 5.7 Hz), 146.58 (d, J = 25.1 Hz), 144.43
(ddd, J = 4.2, 3.1, 1.9 Hz, allyl-C-C-C-H), 134.97 (br s), 134.26 (dd, J
= 40.5, 2.9 Hz), 134.25 (d, J = 2.2 Hz), 133.94 (d, J = 24.6 Hz),
133.93 (s), 133.81 (d, J = 13.6 Hz), 133.47 (dd, J = 39.0, 22.7 Hz),
132.47 (d, J = 11.5 Hz), 132.01 (d, J = 10.2 Hz), 131.65 (d, J = 10.4
Hz), 131.41 (d, J = 45.0 Hz), 131.28 (d, J = 7.6 Hz), 131.16 (d, J =
1.6 Hz), 130.77 (d, J = 2.0 Hz), 130.52 (dd, J = 16.5, 2.7 Hz), 130.38
(d, J = 1.8 Hz), 130.11 (d, J = 11.9 Hz), 129.43 (d, J = 13.0 Hz),
1
(m, 1H); 13C NMR (126 MHz, CDCl3) δC 161.9 (q, J(13C,11B) =
49.8 Hz), 159.2, 149.9 (dd, J = 44.7, 6.2 Hz), 146.0 (d, J = 25.4 Hz),
144.4−144.2 (m), 135.0, 134.4, 134.1 (dd, J = 24.5, 3.5 Hz), 134.1,
133.9 (d, J = 10.6 Hz), 133.8 (d, J = 13.5 Hz), 133.8 (d, J = 2.9 Hz),
133.0−132.8 (m), 132.3 (d, J = 11.3 Hz), 132.1−131.6 (m), 131.6 (d,
J = 10.5 Hz), 130.8 (d, J = 7.6 Hz), 130.7 (dd, J = 43.9, 1.6 Hz),
130.5, 130.2 (d, J = 2.1 Hz), 130.0 (d, J = 11.8 Hz), 129.7 (d, J = 2.3
Hz), 129.4 (d, J = 12.9 Hz), 129.1 (qq, 2J(F,C) = 31.6, 3J(B,C) = 2.9
Hz), 128.8, 128.5 (d, J = 10.3 Hz), 128.3 (d, J = 9.9 Hz), 127.8 (d, J =
8.8 Hz), 127.4 (d, J = 7.2 Hz), 125.7 (d, J = 12.3 Hz), 124.7 (q,
1J(F,C) = 272.5 Hz), 120.4 (d, J = 95.0 Hz), 117.6 (dt, J = 7.3, 3.5
Hz), 113.5, 111.0 (d, J = 96.6 Hz), 109.4 (d, J = 9.6 Hz), 91.9 (dd, J =
17.4, 8.1 Hz), 55.4, 35.9−34.4 (m, allyl-C-C-C-H); 31P NMR (202
MHz, CDCl3) δP 49.63 (ddd, 1JP−Rh = 189.6, 2JP−P = 29.8, 3JP−P = 13.0
Hz), 36.56 (dd, 1JP−Rh = 184.9, 2JP−P = 29.7 Hz), 6.67 (d, 3JP−P = 12.7
Hz). HRMS (ESI-TOF) m/z [M]+ calcd for C64H51OP3Rh
1031.2208; found 1031.2203.
Compound 4a: Prepared from 1 (40 mg, 0.023 mmol) and 1-
octyne (3.4 μL, 0.023 mmol) following general procedure 1; red solid
(42.6 mg, 99%); 1H NMR (500 MHz, CDCl3) δH 7.71 (s, 8H), 7.65
(dd, J = 8.5, 6.6 Hz, 1H), 7.58−7.49 (m, 9H), 7.45 (dd, J = 12.6, 7.7
Hz, 3H), 7.42−7.26 (m, 9H), 7.25−7.10 (m, 8H), 7.06−6.95 (m,
14H), 6.68 (dd, J = 11.2, 7.7 Hz, 2H), 6.24 (dd, J = 8.2, 5.6 Hz, 1H),
3.26 (dd, J = 7.6, 3.9 Hz, 1H), 2.16−2.03 (m, 2H), 1.39−1.22 (m,
2H), 1.08 (qq, J = 13.0, 7.1, 6.5 Hz, 4H), 0.96 (q, J = 7.0 Hz, 2H),
0.80 (t, J = 7.3 Hz, 3H); 13C NMR (126 MHz, CDCl3) δC 161.7 (q, J
= 49.8 Hz), 150.7 (dd, J = 44.0, 5.9 Hz), 145.4 (d, J = 25.7 Hz),
143.8−143.4 (m), 134.8, 134.4 (d, J = 14.1 Hz), 134.3 (d, J = 40.0
Hz), 133.9 (d, J = 10.6 Hz), 133.7 (d, J = 13.7 Hz), 133.7 (dd, J =
63.6, 2.7 Hz), 133.5, 133.3 (d, J = 37.8 Hz), 132.0 (d, J = 11.4 Hz),
131.3, 131.1 (d, J = 10.3 Hz), 130.7−130.3 (m), 130.1−130.0 (m),
129.8 (d, J = 11.9 Hz), 129.5 (d, J = 1.8 Hz), 129.0 (d, J = 12.8 Hz),
128.8 (qq, J = 31.6, 2.6 Hz), 128.2 (dd, J = 11.0 Hz), 128.0 (d, J =
10.0 Hz), 127.3 (d, J = 8.9 Hz), 125.0 (d, J = 12.2 Hz), 124.6 (q, J =
272.6 Hz), 120.1 (d, J = 96.3 Hz), 117.5−117.3 (m), 111.4 (d, J = 8.2
2
3
129.05 (qq,, J(F,C) = 31.3, J(B,C) = 2.7 Hz), 128.59 (d, J = 10.6
Hz), 128.47 (s), 128.32 (d, J = 10.2 Hz), 128.25 (d, J = 10.1 Hz),
126.83 (d, J = 12.1 Hz), 126.77 (dd, J = 75.1, 7.4 Hz), 124.71 (q,
1J(C,F) = 272.6 Hz), 120.31 (d, J = 97.9 Hz), 117.61 (sept, 3J(F,C) =
3.5 Hz), 111.16 (d, J = 95.5 Hz), 90.99 (d, J = 8.8 Hz), 90.03−89.62
(m, allyl-C-C-C-H), 52.83 (s), 28.80−27.40 (m, allyl-C-C-C-H); 31P
NMR (202 MHz, CDCl3) δP 49.80 (ddd, 1JP−Rh = 187.9, 2JP−P = 29.8,
3JP−P = 12.6 Hz), 34.34 (dd, 1JP−Rh = 190.2, 2JP−P = 29.8 Hz), 6.66 (d,
3JP−P = 12.6 Hz); HRMS (ESI-TOF) m/z [M]+ calcd for
C59H47O2P3Rh 983.1844; found 983.1834. Anal. Calcd for
C91H59BF24O2P3Rh: C, 59.17; H, 3.22. Found: C, 59.68; H, 3.75.
Compound 4d: Prepared from 1 (100 mg, 0.023 mmol) and
diphenylacetylene (12.3 mg, 0.069 mmol) following general
procedure 1; red solid (56 mg, 56%); 1H NMR (500 MHz,
CDCl3) δH 7.75 (s, 8H), 7.71−7.63 (m, 3H), 7.59−7.52 (m, 7H),
7.48−7.40 (m, 2H), 7.40−7.26 (m, 10H), 7.26−7.20 (m, 4H), 7.18−
7.14 (m, 3H), 7.09−6.99 (m, 6H), 6.98−6.85 (m, 14H), 6.69 (t, J =
7.3 Hz, 1H), 6.58−6.52 (m, 1H), 6.33 (t, J = 7.7 Hz, 2H), 6.29−6.17
1
(m, 4H); 13C NMR (126 MHz, CDCl3) δC 161.9 (q, J (13C,11B) =
49.8 Hz), 148.8 (dd, J = 45.6, 6.5 Hz), 146.4 (d, J = 24.4 Hz), 142.8−
142.4 (m), 137.7 (d, J = 5.9 Hz, allyl C-C-C-P), 135.9 (d, J = 9.4 Hz),
135.0, 134.9−134.7 (m), 134.4 (dd, J = 7.1, 3.0 Hz), 134.2 (d, J =
12.8 Hz), 134.2 (d, J = 12.9 Hz), 133.9, 133.9 (dd, J = 19.2, 2.8 Hz),
133.5, 133.2 (d, J = 4.9 Hz), 132.7 (d, J = 10.5 Hz), 132.5 (d, J = 9.6
Hz), 131.7−131.3 (m), 131.1 (d, J = 2.4 Hz), 130.9 (d, J = 7.7 Hz),
130.8, 130.3 (d, J = 2.1 Hz), 130.1 (d, J = 2.4 Hz), 129.6 (d, J = 11.5
2
3
Hz), 129.1 (qq, J(F,C) = 31.5, J(B,C) = 2.8 Hz), 128.8 (d, J = 6.4
Hz), 128.6 (d, J = 12.5 Hz), 128.4 (d, J = 10.5 Hz), 128.3 (d, J = 9.7
Hz), 128.3 (d, J = 9.9 Hz), 128.0 (d, J = 8.4 Hz), 127.2, 127.0−126.8
G
Organometallics XXXX, XXX, XXX−XXX