Organometallics
Article
1
2
1
6
7
846, 1600, 1500, 1448, 1399, 1353, 1311, 1260, 1212, 1195, 1096,
059, 1033, 1019, 930, 883, 801, 753, 729, 710, 688, 676, 646, 628,
quantitative yield, mp 125 °C. H NMR (500 MHz, C D , 305 K): δ
6 6
= 0.92 (s, 3 H, C Me ), 1.28 (s, 3 H, C Me ), 1.61−2.46 (14 H, Ad),
5
4
5
4
−
1
2
09, 579 cm . Anal. Calcd for C H PTi: C 81.87, H 7.80; found C
1.74 (s, 3 H, C Me ), 2.12 (s, 4 H, C Me , CH ), 2.65 (d, J = 3.4 Hz,
5
2
59
5 4 5 4 2
1.36, H 7.74.
Synthesis of Ti2e. (NEt ) PCH I (0.517 g, 1.33 mmol) and NaH
1 H, CH ), 3.19 (s, 1 H, CH ), 5.08 (m, 1 H, C H ), 5.14 (m, 1 H,
2 exo 5 4
C H ), 5.94 (m, 1 H, C H ), 6.47 (m, 1 H, C H ) ppm. C NMR
1
3
2
3
3
5
4
5
4
5
4
(
(
0.048 g, 1.99 mmol) were placed in a Schlenk tube, tetrahydrofuran
10 mL) was added, and the resulting suspension was refluxed for 4 h.
(125 MHz, C D , 305 K): δ = 10.9 (C Me ), 11.8 (C Me ), 13.5
(C Me ), 14.5 (C Me ), 28.4 (Ad CH), 28.6 (Ad CH), 32.5 (Ad
5 4 5 4
6 6 5 4 5 4
After cooling to room temperature, the suspension was filtered into a
Schlenk tube containing a solution of Ti1b (0.500 g, 0.89 mmol) in 2
mL of tetrahydrofuran. The former blue solution turns brown and was
stirred overnight at room temperature. Evaporation of the solvent and
drying in vacuo afforded Ti2e in quantitative yield as a dark red-
brown solid, mp 83 °C (dec.). H NMR (500 MHz, C D , 305 K): δ
=
CH), 32.8 (Ad CH ), 32.9 (Ad CH ), 33.1 (Ad CH), 38.4 (Ad CH ),
2
2
2
39.0 (Ad CH ), 39.1 (Ad CH ), 45.3 (CH ), 75.4 (CH ), 106.8
2
2
exo
2
(C H ), 109.7 (C H ), 111.4 (C H ), 118.7 (C H ), 121.2 (C Me ),
5
4
5
4
5
4
5
4
5
4
126.5 (C Me ), 128.6 (C Me ), 130.2 (C Me ), 133.7 (CipsoCp),
5
4
5
4
5
4
135.6 (C Me ) ppm. IR (ATR, 16 scans): v
̃
= 2963, 2902, 2848, 1468,
5
4
1
1449, 1377, 1260, 1089, 1061, 1017, 874, 795, 745, 693, 619, 603,
6
6
−
1
0.85−0.88 (m, 18 H, CH ), 2.08 (s, 3 H, CH ), 2.11 (s, 3 H, CH ),
580 cm .
Synthesis of Ti5. Ti3 (0.500 g, 1.2 mmol) and Y1 (0.331 g, 1.2
3
3
3
2
.15 (s, 6 H, CH ), 2.67−2.75 (m, 6 H, CH ), 2.82−2.91 (m, 6 H,
3
2
CH ), 4.43 (m, 1 H, C H ), 4.76 (m, 1 H, C H ), 4.80 (m, 1 H,
C H ), 4.83 (m, 1 H, C H ), 5.12 (s, 1 H, CHexo), 5.56 (m, 1 H,
C H ), 6.47 (m, 1 H, C H ), 6.70 (m, 1 H, C H ), 6.82−6.84 (m, 3
H, C H + pTol CH), 6.92 (m, 1 H, CH ), 6.94 (m, 6 H, pTol CH),
mmol) were placed in a Schlenk tube and 10 mL of n-hexane was
added. The resulting red suspension was stirred for 8 h at room
temperature and subsequently an excess acetone was added. After
storing at 60 °C overnight, the resulting yellow suspension was
filtrated to remove triphenylphosphine oxide (0.196 g, 0.7 mmol,
59%). The solvent was evaporated and the resulting yellow solid dried
in vacuo, yielding 0.361 g (0.76 mmol, 63%) of Ti5, mp 156 °C.
Single crystals suitable for X-ray diffraction could be obtained from a
2
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
Ylid
7
.11 (d, J = 7.6 Hz, 2 H, pTol CH), 7.23 (d, J = 7.7 Hz, 2 H, pTol
CH), 7.59 (d, J = 7.8 Hz, 2 H, pTol CH), 7.65 (d, J = 7.6 Hz, 2 H,
pTol CH) ppm. 13C NMR (125 MHz, C D , 305 K): δ = 14.2
6
6
(NCH CH ), 14.3 (NCH CH ), 21.0 (CH ), 40.2 (NCH CH ),
2 3 2 3 3Tol 2 3
1
4
0.2 (NCH CH ), 52.1 (CH ), 105.1 (C H ), 105.1 (C H ), 106.2
saturated solution of Ti5 in n-hexane at 5 °C. H NMR (500 MHz,
2
3
exo
5
4
5
4
(C H ), 107.5 (C H ), 107.5 (C H ), 108.6 (Fv C ), 109.2 (C H ),
C D , 305 K): δ = 1.23 (s, 3 H, OC(CH3) ), 1.48 (s, 3 H,
5
4
5
4
5
4
exo
5
4
6
6
2
1
10.0 (C H ), 111.4 (C H ), 113.4 (C H ), 123.3 (pTol C), 123.3
OC(CH3) ), 1.50−2.41 (14 H, Ad), 1.53 (s, 3 H, C Me ), 1.69 (s, 3
5
4
5
4
5
4
2
5
4
3
(Cipso Cp), 127.1 (pTol CH), 127.5 (pTol CH), 128.6 (pTol CH),
H, C Me ), 1.72 (s, 3 H, C Me ), 2.33 (d, J = 13.2 Hz, 1 H, CH ),
5 4 5 4 CH 2
3
1
29.0 (pTol CH), 129.0 (pTol CH), 129.2 (pTol CH), 129.5 (pTol
2.36 (s, 3 H, C Me ), 2.70 (d, J = 13.2 Hz, 1 H, CH ), 3.21 (s, 1
5 4 CH 2
CH), 132.4 (pTol C), 132.6 (pTol CH), 133.0 (pTol C), 135.3 (pTol
C), 135.6 (pTol C), 142.7 (pTol C), 144.2 (pTol C), 145.2 (pTol C),
H, CHexo), 5.53 (m, 1 H, C H ), 5.59 (m, 1 H, C H ), 5.84 (m, 1 H,
5 4 5 4
1
3
C H ), 6.49 (m, 1 H, C H ) ppm. C NMR (125 MHz, C D , 305
5
4
5
4
6
6
1
31
1
47.1 (pTol C), 151.0 (d, J = 62.7 Hz, CHylide) ppm. P NMR
K): δ = 11.5 (C Me ), 12.8 (C Me ), 13.1 (C Me ), 14.2 (C Me ),
5 4 5 4 5 4 5 4
PC
(202 MHz, C D , 305 K): δ = 56.6 ppm. IR (ATR, 16 scans): v
̃
=
28.5 (2 × Ad CH), 32.0 (OC(CH3) ), 32.0 (Ad CH), 32.6 (Ad CH),
6
6
2
2
1
969, 2921, 2870, 1508, 1455, 1379, 1295, 1260, 1203, 1172, 1054,
33.0 (Ad CH ), 33.0 (Ad CH ), 34.5 (OC(CH3) ), 38.4 (CH ), 38.7
2
2
2
2
−1
017, 946, 924, 864, 796, 762, 737, 688, 638, 569 cm .
(CH ), 39.1 (CH ), 39.3 (CH ), 44.1 (CH ), 108.6 (OC(CH ) ),
2 2 2 exo 3 2
Synthesis of Ti4a and Ti4b. Ti3 (0.500 g, 1.2 mmol) and Y1
0.331 g, 1.2 mmol) were placed in a Schlenk tube and n-hexane (10
109.7 (C H ), 111.9 (C H ), 114.9 (C H ), 115.6 (C Me ), 116.4
5 4 5 4 5 4 5 4
(C Me ), 121.1 (C H ), 121.8 (C Me ), 132.1 (C Me ), 138.2
5 4 5 4 5 4 5 4
(
mL) was added. The former blue suspension turns red and was stirred
at room temperature overnight. Subsequently, the mother liquor was
decanted and the solid washed with n-hexane (2 × 3 mL). Drying in
vacuo only afforded a mixture of two products being subject to a
reversible thermodynamic equilibrium. In this, the two compounds
Ti4a and Ti4b are present in the ratio of 1:1. Increasing the
temperature (353 K), the equilibrium can be influenced in favor of
compound Ti4b. Combined data for Ti4a and Ti4b were as follows.
(CipsoCp), 140.8 (C Me ) ppm. IR (ATR, 16 scans): v
2875, 2849, 1488, 1449, 1377, 1359, 1292, 1255, 1194, 1143, 1113,
̃
= 2965, 2902,
5
4
−
1
1100, 1058, 1023, 965, 909, 852, 806, 778, 691, 608, 595, 572 cm .
Anal. Calcd for C H ClOTi: C 70.81, H 8.28; found C 71.05, H
2
8
39
8.38.
Synthesis of Ti6. Ti3 (0.250 g, 0.6 mmol) and Y1 (0.166 g, 0.6
mmol) were placed in a Schlenk tube and 7 mL of n-hexane was
added. The resulting red suspension was stirred for 8 h at room
temperature and subsequently ferrocenealdehyde (0.128 g, 0.6 mmol)
was added. After storing at 60 °C overnight, single crystals suitable for
X-ray diffraction could be obtained from the reaction mixture. The
mother liquor was decanted and the red crystals dried in vacuo,
1
H NMR (500 MHz, C D , 303 K): δ = 0.93 (s, 3 H, C Me ), 1.29 (s,
6
6
5
4
3
H, C Me ), 1.47−2.47 (Ad), 1.74 (s, 3 H, C Me ), 2.04 (s, 15 H,
5
4
5
4
2
C Me ), 2.12 (s, 3 H, C Me ), 2.13 (m, 1 H, CH ), 2.65 (d, J = 3.5
5
5
5
4
2
Hz, 1 H, CH ), 3.19 (s, 1 H, CHexo), 3.27 (s, 1 H, CHexo), 4.77 (m, 1
2
1
H, C H ), 5.08 (m, 1 H, C H ), 5.14 (m, 1 H, C H ), 5.19 (m, 1 H,
yielding 0.104 g (0.16 mmol, 27%) of Ti6, mp 135 °C. H NMR (500
5
4
5
4
5
4
C H ), 5.72 (m, 1 H, C H ), 5.95 (m, 2 H, C H ), 6.48 (m, 1 H,
MHz, C D , 305 K): δ = 1.49−2.44 (14 H, Ad), 1.55 (s, 3 H, C Me ),
5
4
5
4
5
4
6
6
5
4
C H ), 7.02−7.11 (m, 18 H, C H ), 7.71−7.75 (m, 12 H, C H ), 9.01
1.69 (s, 3 H, C Me ), 1.72 (s, 3 H, C Me ), 2.44 (s, 3 H, C Me ), 2.47
5
4
6
5
6
5
5 4 5 4 5 4
(dd, J = 12.8, J = 10.3 Hz, 1 H, CH ), 3.07 (dd, J = 12.9 Hz,
CH CH 2 CH
2
13
2
3
2
(
1
(
d, J = 4.8 Hz, CH) ppm. C NMR (125 MHz, C D , 303 K): δ =
PH
6
6
3
0.9 (C Me ), 11.8 (C Me ), 13.5 (Cp*), 13.5 (C Me ), 14.5
JCH = 6.1 Hz, 1 H, CH ), 3.29 (s, 1 H, CHexo), 4.01 (m, 2 H,
5
4
5
4
5
4
2
C Me ), 28.4 (Ad CH), 28.6 (Ad CH), 28.6 (Ad CH), 28.6 (Ad
FcC H ), 4.11 (s, 5 H, FcC H ), 4.12 (m, 2 H, FeC H ), 5.58 (m, 1
5 4 5 5 5 4
5
4
3
CH), 32.4 (Ad CH ), 32.5 (Ad CH ), 32.8 (Ad CH ), 32.9 (Ad
H, C H ), 5.72 (m, 1 H, C H ), 5.93 (m, 1 H, C H ), 6.28 (dd, J
=
2
2
2
5
4
5
4
5
4
CH
1
3
CH ), 33.0 (Ad CH), 33.0 (Ad CH ), 33.1 (Ad CH), 33.2 (Ad CH ),
10.3 Hz, 6.1 Hz, 1 H, FcCHO), 6.47 (m, 1 H, C H ) ppm. C NMR
2
2
2
5 4
3
8.4 (Ad CH ), 38.7 (Ad CH ), 39.0 (Ad CH ), 39.1 (Ad CH ), 39.2
(125 MHz, C D , 305 K): δ = 11.4 (C Me ), 12.7 (C Me ), 12.9
6 6 5 4 5 4
2
2
2
2
(Ad CH ), 39.3 (Ad CH ), 44.1 (CHexo), 45.9 (CHexo), 75.4 (CH2),
(C Me ), 13.6 (C Me ), 28.4 (Ad CH), 28.5 (Ad CH), 32.0 (Ad
2
2
5 4 5 4
04.9 (C H ), 106.8 (C H ), 107.7 (C H ), 108.4 (C H ), 19.7
CH), 32.5 (Ad CH), 33.0 (Ad CH ), 33.4 (CH ), 38.4 (Ad CH ),
2 2 2
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
4
5
5
38.8 (Ad CH ), 39.0 (Ad CH ), 43.7 (CHexo), 66.6 (FcCH), 67.8
2
2
21.2 (C Me4), 126.5 (C Me4), 128.4 (d, J = 12.7 Hz, PPh ), 128.54
(FcCH), 67.9 (FcCH), 68.0 (FcCH), 69.0 (FcCH), 92.9 (FcC), 97.4
(FcCHO), 110.6 (C H ), 112.7 (C H ), 115.7 (C H ), 116.2
5
5
3
3 5 4 3
5
4
5
4
5
4
1
9
31.0 (d, J = 2.8 Hz, PPh ), 132.7 (d, J = 9.0 Hz, PPh ), 133.7 (d, J =
(C Me ), 117.7 (C Me ), 120.1 (C H ), 121.3 (C Me ), 131.5
3
3
5 4 5 4 5 4 5 4
1
.3 Hz, PPh ), 133.7 (C Cp), 134.3 (d, J = 80.0 Hz, PPh ), 135.3
(C Me ), 138.5 (C C Me ), 139.4 (CipsoCp) ppm. IR (ATR, 16
5 4 ipso 5 4
3
ipso
PC
3
1
(
d, J = 84.1 Hz, PPh ), 135.5 (C Cp), 136.1 (C Me4), 173.5 (d,
scans): v
̃ = 3094, 2902, 2846, 1487, 1467, 1448, 1411, 1378, 1354,
PC
3
ipso
5
1
JPC = 29.1 Hz, CHylide) ppm.
1332, 1293, 1260, 1105, 1058, 1035, 1015, 1002, 972, 955, 933, 883,
−
1
Synthesis of Ti4b. Ti3 (1 g, 2.4 mmol) and Y1 (0.020 g, 0.072
mmol) were placed in a Schlenk tube, 10 mL of n-hexane was added,
and the resulting red suspension was stored at 60 °C overnight.
Evaporation of the solvent and drying in vacuo afforded Ti4b in
850, 827, 806, 781, 721, 690, 685, 646, 632, 604, 586 cm . Anal.
Calcd for C H ClFeOTi: C 68.54, H 6.87; found C 70.63, H 6.29.
3
6
43
Synthesis of Ti7. Ti3 (0.250 g, 0.6 mmol) and catalytic amounts
of Y1 were placed in a Schlenk tube and 7 mL of n-hexane was added.
J
Organometallics XXXX, XXX, XXX−XXX