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Compound 5c: Yield: 0.091 g, 66%; 1H NMR (CDCl3): d=5.03 (s,
General procedure for the synthesis of complexes 4a–c, 5a,
5c, 5d, and 6a–d
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3H; C6H3Me3), 4.23 (dt, J(H,P)=12.1 Hz, J(H,H)=7.0 Hz, 4H; OCH2),
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2.24 (s, 9H; C6H3Me3), 1.37 ppm (t, J(H,H)=7.0 Hz, 6H; OCH2CH3),
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OH signal not observed; 13C{1H} NMR (CDCl3): d=106.4 (d, J(C,P)=
The corresponding [{RuCl(m-Cl)(h6-arene)}2] dimer 1a–d (0.16 mmol)
was partially dissolved in THF (15 mL), and treated at 708C with
the appropriate disubstituted phosphite (RO)2P(=O)H (0.80 mmol)
for 2 h. The resulting solution was then evaporated to dryness and
the oily residue formed dissolved in diethyl ether (50 mL; at this
point, for some complexes, it may be that no solid is dissolved and
the solution remains clear; in these cases, the solid was washed
with diethyl ether several times and dried under vacuum). The mix-
ture was filtered through Celite and the filtrate was evaporated to
dryness. The syrup thus formed was dissolved in the minimum
amount of dichloromethane (ca. 5 mL), and the desired product
precipitated from the solution as an orange–reddish solid by
adding hexane (30 mL). The solid was filtered, washed with hexane
(210 mL), and dried under vacuum.
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2.7 Hz; C of C6H3Me3), 84.3 (d, J(C,P)=5.8 Hz; CH of C6H3Me3), 62.9
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(d, J(C,P)=7.3 Hz; OCH2), 19.0 (s; C6H3Me3), 16.4 ppm (d, J(C,P)=
5.8 Hz; OCH2CH3); 31P{1H} NMR (CDCl3): d=114.8 ppm (s); IR (KBr):
n˜ =3269 (br), 3050 (w), 2977 (w), 2923 (w), 1521 (m), 1448 (m),
1384 (m), 1262 (m), 1120 (s), 1099 (s), 1054 (s), 1029 (vs), 960 (m),
938 (s), 880 (vs), 779 (w), 736 (m), 545 cmÀ1 (m); elemental analysis
calcd (%) for C13H23O3Cl2PRu: C 36.29, H 5.39; found: C 36.33, H
5.60.
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Compound 5d: Yield: 0.097 g, 64%; H NMR (CDCl3): d=4.25–4.10
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(m, 4H; OCH2), 2.10 (d, J(H,P)=1.2 Hz, 18H; C6Me6), 1.34 ppm (t,
3J(H,H)=7.1 Hz, 6H; OCH2CH3), OH signal not observed;
13C{1H} NMR (CDCl3): d=97.8 (d, 2J(C,P)=4.4 Hz; C6Me6), 62.4 (d,
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2J(C,P)=8.0 Hz; OCH2), 16.2 (d, J(C,P)=6.0 Hz; OCH2CH3), 15.8 ppm
(s; C6Me6); 31P{1H} NMR (CDCl3): d=116.2 ppm (s); IR (KBr): n˜ =3254
(br), 2983 (s), 2907 (m), 1442 (m), 1385 (s), 1261 (w), 1122 (s), 1045
(vs), 1025 (vs), 954 (vs), 876 (vs), 777 (s), 752 (s), 553 (m), 536 cmÀ1
(m); elemental analysis calcd (%) for C16H29O3Cl2PRu: C 40.68, H
6.19; found: C 40.59, H 6.09.
Compound 4a: Yield: 0.101 g, 88%; 1H NMR (CDCl3): d=5.78 (s,
6H; C6H6), 3.87 ppm (d, J(H,P)=11.2 Hz, 6H; OMe), OH signal not
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observed; 13C{1H} NMR (CDCl3): d=89.2 (d, 2J(C,P)=4.5 Hz; C6H6),
54.2 ppm (d, 2J(C,P)=7.5 Hz; OMe); IR (KBr): n˜ =3063 (br), 3014 (m),
2944 (m), 2833 (w), 1515 (w), 1434 (m), 1176 (m), 1142 (m), 1054
(s), 1023 (vs), 896 (vs), 835 (m), 802 (s), 771 (s), 615 (w), 550 cmÀ1
(s); 31P{1H} NMR (CDCl3): d=114.4 ppm (s); elemental analysis calcd
(%) for C8H13O3Cl2PRu: C 26.68, H 3.64; found: C 26.77, H 3.56.
Compound 6a: Yield: 0.098 g, 63%; 1H NMR (CDCl3): d=7.41 (m,
10H; OPh), 5.52 ppm (s, 6H; C6H6), OH signal not observed;
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13C{1H} NMR (CDCl3): d=151.2 (d, J(C,P)=9.3 Hz; C of OPh), 129.8
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Compound 4b:[16] Yield: 0.114 g, 86%; H NMR (CDCl3): d=5.61 (d,
(s; CH of OPh), 125.5 (s; CH of OPh), 121.5 (d, J(C,P)=4.3 Hz; C of
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OPh), 89.4 ppm (d, J(C,P)=4.3 Hz; C6H6); 31P{1H} NMR (CDCl3): d=
3J(H,H)=6.0 Hz, 2H; CH of cymene), 5.48 (d, 3J(H,H)=6.0 Hz, 2H;
CH of cymene), 3.85 (d, 3J(H,P)=11.2 Hz, 6H; OMe), 2.88 (sept,
3J(H,H)=6.9 Hz, 1H; CHMe2), 2.20 (s, 3H; Me), 1.27 ppm (d,
3J(H,H)=6.9 Hz, 6H; CHMe2), OH signal not observed; 13C{1H} NMR
(CDCl3): d=108.1 (s; C of cymene), 101.5 (s; C of cymene), 88.8 (d,
2J(C,P)=6.2 Hz; CH of cymene), 88.1 (d, 2J(C,P)=5.5 Hz; CH of
cymene), 54.0 (d, 2J(C,P)=8.0 Hz; OMe), 30.7 (s; CHMe2), 22.0 (s;
CHMe2), 18.6 ppm (s, Me); 31P{1H} NMR (CDCl3): d=115.6 ppm (s); IR
(KBr): n˜ =3412 (br), 3113 (w), 3040 (w), 2952 (m), 2873 (w), 1461
(m), 1389 (m), 1324 (w), 1175 (s), 1159 (s), 1093 (s), 1029 (vs), 911
(s), 886 (s), 866 (m), 802 (s), 758 (s), 535 cmÀ1 (m); elemental analy-
sis calcd (%) for C12H21O3Cl2PRu: C 34.63, H 5.09; found: C 34.52, H
5.13.
114.0 ppm (s); IR (KBr): n˜ =3115 (br), 3069 (w), 3041 (w), 1586 (s),
1487 (vs), 1435 (m), 1206 (vs), 1180 (s), 1161 (m), 1069 (w), 1024
(m), 910 (vs), 893 (vs), 819 (w), 764 (s), 723 (w), 691 (m), 595 (m),
493 cmÀ1 (m); elemental analysis calcd (%) for C18H17O3Cl2PRu: C
44.64, H 3.54; found: C 44.65, H 3.61.
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Compound 6b: Yield: 0.112 g, 65%; H NMR (CDCl3): d=7.40–7.20
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(m, 10H; Ph), 6.68 (brs, 1H; OH), 5.60 (d, J(H,H)=6.0 Hz, 2H; CH
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of cymene), 5.33 (d, J(H,H)=6.0 Hz, 2H; CH of cymene), 2.86 (sept,
3J(H,H)=6.9 Hz, 1H; CHMe2), 2.01 (s, 3H; Me), 1.26 ppm (d,
3J(H,H)=6.9 Hz, 6H; CHMe2); 13C{1H} NMR (CDCl3): d=151.3 (d,
2J(C,P)=11.5 Hz; C of Ph), 129.7 (s; CH of Ph), 125.2 (s; CH of Ph),
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121.3 (d, J(C,P)=4.3 Hz; C of Ph), 108.4 (s; C of cymene), 102.4 (s;
C of cymene), 88.8 (d, 2J(C,P)=6.6 Hz; CH of cymene), 88.4 (d,
2J(C,P)=5.6 Hz; CH of cymene), 30.8 (s; CHMe2), 22.1 (s; CHMe2),
18.4 ppm (s; Me); 31P{1H} NMR (CDCl3): d=112.9 ppm (s); IR (KBr):
n˜ =3173 (br), 3072 (w), 3041 (m), 2964 (w), 2872 (w), 1590 (s), 1492
(vs), 1385 (m), 1211 (vs), 1196 (vs), 1118 (s), 1028 (s), 1006 (w), 922
(vs), 905 (vs), 770 (s), 753 (s), 720 (m), 690 (s), 618 (m), 586 (m), 496
(m), 480 cmÀ1 (m); elemental analysis calcd (%) for C22H25O3Cl2PRu:
C 48.90, H 4.66; found: C 48.70, H 4.69.
Compound 4c: Yield: 0.084 g, 65%; 1H NMR (CDCl3): d=5.06 (s,
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3H; C6H3Me3), 3.85 (d, J(H,P)=11.0 Hz, 6H; OMe), 2.25 ppm (s, 9H;
C6H3Me3), OH signal not observed; 13C{1H} NMR (CDCl3): d=106.9
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(s; C of C6H3Me3), 84.2 (d, J(C,P)=5.5 Hz; CH of C6H3Me3), 53.6 (d,
2J(C,P)=7.1 Hz; OMe), 19.0 ppm (s; C6H3Me3); IR (KBr): n˜ =3258 (br),
3020 (w), 2951 (m), 2847 (w), 1522 (m), 1451 (m), 1379 (m), 1182
(w), 1120 (s), 1056 (s), 1011 (vs), 883 (s), 797 (s), 763 (s), 643 (w),
539 cmÀ1 (m); 31P{1H} NMR (CDCl3): d=117.9 ppm (s); elemental
analysis calcd (%) for C11H19O3Cl2PRu: C 32.85, H 4.76; found: C
32.78, H 4.74.
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Compound 6c: Yield: 0.101 g, 60%; H NMR (CDCl3): d=7.36–7.26
(m, 8H; Ph), 7.18 (m, 2H; Ph), 4.98 (s, 3H; C6H3Me3), 2.20 ppm (s,
9H; C6H3Me3), OH signal not observed; 13C{1H} NMR (CDCl3): d=
Compound 5a: Yield: 0.096 g, 77%; 1H NMR (CDCl3): d=5.74 (s,
6H; C6H6), 4.25 (dt, 3J(H,P)=14.6 Hz, 3J(H,H)=7.1 Hz, 4H; OCH2),
1.38 ppm (t, 3J(H,H)=7.1 Hz, 6H; OCH2CH3), OH signal not ob-
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151.3 (d, J(C,P)=11.4 Hz; C of Ph), 129.6 (s; CH of Ph), 124.9 (s; CH
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of Ph), 121.1 (d, J(C,P)=4.4 Hz; C of Ph), 107.4 (s; C of C6H3Me3),
84.7 (d, 2J(C,P)=5.8 Hz; CH of C6H3Me3), 19.1 ppm (s; C6H3Me3);
31P{1H} NMR (CDCl3): d=112.7 ppm (s); IR (KBr): n˜ =3400 (br), 3056
(w), 2968 (w), 2918 (w), 1589 (s), 1527 (w), 1488 (vs), 1453 (m),
1376 (w), 1218 (m), 1189 (vs), 1160 (m), 1071 (w), 1025 (m), 1006
(w), 900 (vs), 763 (s), 730 (m), 691 (s), 593 (m), 497 cmÀ1 (m); ele-
mental analysis calcd (%) for C21H23O3Cl2PRu: C 47.92, H 4.40;
found: C 47.83, H 4.54.
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served; 13C{1H} NMR (CDCl3): d=89.2 (d, J(C,P)=4.4 Hz; C6H6), 63.5
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(d, J(C,P)=7.5 Hz; OCH2), 16.4 ppm (d, J(C,P)=5.9 Hz; OCH2CH3);
31P{1H} NMR (CDCl3): d=110.8 ppm (s); IR (KBr): n˜ =3400 (br), 3076
(m), 2981 (m), 2929 (w), 2904 (w), 1434 (m), 1389 (m), 1178 (m),
1043 (vs), 1022 (vs), 956 (s), 903 (s), 880 (w), 816 (m), 789 (m), 751
(w), 613 (w), 549 cmÀ1 (m); elemental analysis calcd (%) for
C10H17O3Cl2PRu: C 30.94, H 4.41; found: C 30.82, H 4.49.
Chem. Eur. J. 2015, 21, 16874 – 16886
16883
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