Organometallics
Article
MHz, DMSO-d6): δ 7.45 (t, 4JHH = 1.9 Hz, 1H, Ar-H), 7.40 (dd, 3JHH
= 7.6 Hz, 4JHH = 1.7 Hz, 1H, Ar-H), 7.37 (d, 4JHH = 1.9 Hz, 2H, Ar-H),
6.62 (t, 3JHH = 7.5 Hz, 1H, Ar-H), 6.55 (dd, 3JHH = 7.3 Hz, 4JHH = 1.7
Hz, 1H, Ar-H), 3.98 (s, 4H, 2NH2), 2.63 (s, 4H, alkyl backbone).
13C{1H} NMR (101 MHz, DMSO-d6): δ 149.09, 147.60, 144.08,
139.02, 132.72, 130.06, 128.21, 125.26, 122.40, 120.02, 40.44. HRMS
(FAB+): [M]+ C14H14Cl2N2S2Zn calculated 407.9267, found
407.9269. FTIR (neat): 3498, 3293, 3227, 3196, 3106, 2981, 1594,
1561, 1414, 1368, 1281, 1094, 1030, 855, 783, 771, 693, 660 cm−1.
Zinc Phenanthrene-3,4-dithiolate (Zn-V). This compound was
synthesized according to the representative procedure; the reaction
was conducted on a 5.46 mmol scale. Zinc dithiolate Zn-V was formed
as a white powder (0.759 g, 38% yield). 1H NMR (400 MHz, DMSO-
d6): δ 11.15 (d, 3JHH = 8.5 Hz, 1H, Ar-H), 7.77 (t, 3JHH = 7.9 Hz, 2H,
d8): δ 14.10 (s, 0.35H, down-benzylidene H), 14.05 (s, 0.65H, up-
benzylidene H), 7.79−7.68 (m, 1H, Ar-H), 7.45−7.34 (m, 2H, Ar-H),
3
7.32−7.03 (m, 5H, Ar-H), 6.91 (s(br), 2H, Ar-H), 6.76 (t, JHH = 7.5
Hz, 1H, Ar-H), 6.74−6.69 (m, 1H, Ar-H), 6.65 (d, 3JHH = 4.5 Hz, 1H,
Ar-H), 6.61−6.57 (m, 1H, Ar-H), 6.57−6.52 (m, 1H, Ar-H), 6.19 (s,
3
1H, Ar-H), 5.26 (hept, JHH = 6.6 Hz, 0.35H, down−methine), 5.15
(hept, J = 6.6 Hz, 0.65H, up-methine), 3.97−3.69 (m, 4H, NHC-
methylenes), 2.51 (s, 3H, Ar-methyl), 2.45−2.33 (m, 5H, Ar-methyl),
3
2.25−2.17 (m, 7H, Ar-methyl), 2.11 (s, 3H, Ar-methyl), 1.62 (d, JHH
i
3
i
= 6.6 Hz, 1H, Pr-methyl), 1.57 (d, JHH = 6.5 Hz, 2H, Pr-methyl),
1.45 (t, 3JHH = 6.5 Hz, 2H, iPr-methyl), 1.31 (d, 3JHH = 6.5 Hz, 1H, iPr-
methyl). 13C{1H} NMR (101 MHz, THF-d8): δ 248.29, 246.95,
220.61, 220.44, 156.21, 155.68, 155.36, 151.95, 145.07, 144.97, 144.04,
143.04, 142.99, 141.14, 140.86, 140.39, 139.27, 139.08, 137.87, 137.75,
136.90, 136.34, 131.11, 130.82, 130.28, 129.84, 128.34, 128.04, 127.71,
127.30, 127.21, 126.99, 126.65, 126.49, 125.07, 124.77, 123.31, 122.82,
122.77, 122.53, 122.13, 120.78, 116.52, 115.96, 82.06, 80.74, 52.15,
26.02, 24.46, 23.92, 22.29, 21.60, 21.28, 19.98, 19.38, 17.95. HRMS
(FAB+): [M]+ C43H46N2OS2Ru calculated 772.2096, found 772.2080.
Ruthenium Catalyst IV. This compound was synthesized according
to the representative procedure; the reaction was conducted on a
0.0253 mmol scale. Ruthenium catalyst IV was formed as a brown
solid (19 mg, 88% yield) and mixture of isomers. 1H NMR (500 MHz,
THF-d8): δ 14.21 (s, 0.33H, down-benzylidene H), 14.07 (s, 0.67H,
up-benzylidene H), 7.75 (d, 3JHH = 2.0 Hz, 1H, Ar-H), 7.46−7.42 (m,
3
Ar-H), 7.61−7.31 (m, 4H, Ar-H), 7.16 (d, JHH = 8.1 Hz, 1H, Ar-H),
4.10 (s, 4H, 2NH2), 2.72 (s, 4H, alkyl backbone). 13C{1H} NMR (101
MHz, DMSO-d6): δ 147.45, 141.87, 133.09, 131.92, 131.05, 129.82,
129.57, 128.65, 127.86, 127.16, 124.95, 123.91, 122.71, 120.77, 40.52.
HRMS (FAB+): [M]+ C16H16N2S2Zn calculated 364.0046, found
364.0039. FTIR (neat): 3318, 3241, 3191, 3120, 3062, 2947, 1570,
1442, 1281, 1189, 1165, 1129, 1030, 838, 794, 748 cm−1.
Zinc 6-Methylphenanthrene-3,4-dithiolate (Zn-VI). This com-
pound was synthesized according to the representative procedure; the
reaction was conducted on a 1.56 mmol scale. Zinc dithiolate Zn-VI
1
was formed as a white powder (0.365 g, 62% yield). H NMR (400
3
3
1H, Ar-H), 7.38 (t, JHH = 2.0 Hz, 1H, Ar-H), 7.30−7.23 (m, 1.67H,
MHz, DMSO-d6): δ 11.04 (s, 1H, Ar-H), 7.74 (d, JHH = 8.0 Hz, 1H,
3
Ar-H), 7.23−7.20 (m, 0.33H, Ar-H), 7.18−7.15 (m, 1H, Ar-H), 6.94
(s(br), 2H, Ar-H), 6.82−6.72 (m, 1.67H, Ar-H), 6.71−6.65 (m, 1H,
Ar-H), 6.64−6.60 (m, 1H, Ar-H), 6.56 (dd, 3JHH = 7.5, 1.6 Hz, 0.33H,
Ar-H), 7.67 (d, JHH = 8.0 Hz, 1H, Ar-H), 7.43 (s, 2H, Ar-H), 7.30
(dd, 3JHH = 8.0, 4.0 Hz, 1H, Ar-H), 7.13 (d, 3JHH = 8.0 Hz, 1H, Ar-H),
4.10 (s, 4H, 2NH2), 2.71 (s, 4H, alkyl backbone), 2.49 (s, 3H, Ar-
methyl). 13C{1H} NMR (101 MHz, DMSO-d6): δ 147.17, 141.89,
132.02, 131.61, 131.08, 130.89, 129.78, 128.54, 127.08, 126.97, 126.43,
123.79, 120.79, 40.47, 22.07. HRMS (FAB+): [M]+ C17H18N2S2Zn
calculated 378.0203, found 378.0201. FTIR (neat): 3328, 3221, 2952,
1594, 1525, 1378, 1300, 1190, 1047, 843 cm−1.
3
Ar-H), 6.21 (s, 1H, Ar-H), 5.30 (hept, JHH = 6.5 Hz, 0.33H, down-
3
methine), 5.14 (hept, JHH = 6.5 Hz, 0.67H, up-methine), 4.08−3.69
(m, 4H, NHC-methylenes), 2.76 (s, 1H, Ar-methyl), 2.52 (s, 2H, Ar-
methyl), 2.50−2.40 (m, 5H, Ar-methyl), 2.23 (s, 5H, Ar-methyl), 2.18
(s, 2H, Ar-methyl), 2.12 (s, 2H, Ar-methyl), 1.83−1.75 (m, 1H, Ar-
3
i
3
methyl), 1.69 (d, JHH = 6.7 Hz, 1H, Pr-methyl), 1.59 (d, JHH = 6.5
Representative Procedures for the Synthesis of Ruthenium
Dithiolates II−VII. This procedure was adapted from Hoveyda et al.54
In a nitrogen-filled glovebox, an oven-dried vial equipped with a
magnetic stir bar was charged with GH-II (1.0 equiv), Zn-xx (2.0
equiv), and tetrahydrofuran (0.08 M with respect to GH-II). The
reaction mixture was stirred for 5 h at ambient temperature. The
reaction mixture was concentrated, dissolved in dichloromethane,
filtered through a Celite plug, and concentrated to deliver the desired
product.
Hz, 2H, Pr-methyl), 1.45 (d, 3JHH = 6.5 Hz, 2H, iPr-methyl), 1.35 (d,
i
3JHH = 6.5 Hz, 1H, iPr-methyl). 13C{1H} NMR (126 MHz, THF-d8): δ
249.55, 248.67, 219.92, 157.08, 155.76, 155.35, 152.03, 148.27, 144.83,
142.95, 140.38, 139.09, 138.16, 137.84, 137.35, 137.01, 136.32, 134.61,
134.24, 130.91, 130.37, 129.93, 129.70, 129.49, 129.38, 129.17, 128.27,
127.58, 127.29, 126.62, 126.41, 125.15, 124.83, 123.20, 122.93, 122.36,
122.03, 121.05, 116.84, 116.07, 82.69, 81.20, 52.23, 41.75, 24.00,
22.24, 21.62, 21.27, 20.02, 19.83, 19.41, 17.92. HRMS (FAB+): [(M]+
C43H44Cl2N2OS2Ru calculated 840.1316, found 840.1349.
Ruthenium Catalyst II. This compound was synthesized according
to the representative procedure; the reaction was conducted on a
0.0253 mmol scale. Ruthenium catalyst II was formed as a brown solid
Ruthenium Catalyst V. This compound was synthesized according
to the representative procedure; the reaction was conducted on a 0.68
mmol scale. Ruthenium catalyst V was formed as a brown solid (502
mg, 92% yield) and mixture of isomers. H NMR (400 MHz, CDCl3):
δ 14.05 (s, 0.28H, down-benzylidene H), 13.97 (s, 0.72H, up-
1
(18 mg, 95% yield) and a mixture of isomers. H NMR (400 MHz,
THF-d8): δ 14.21 (s, 0.5H, down-benzylidene H), 14.11 (s, 0.5H, up-
3
3
benzylidene, H), 8.81 (d, JHH = 8.3 Hz, 0.5H, Ar-H), 8.32 (d, JHH
=
8.3 Hz, 0.5H, Ar-H), 7.59 (d, 3JHH = 8.0 Hz, 0.5H, Ar-H), 7.54 (d, 3JHH
3
benzylidene H), 11.72 (d, JHH = 8.6 Hz, 0.75H, Ar-H), 10.87−10.78
3
(m, 0.29H, Ar-H), 7.83 (dd, 3JHH = 7.8 Hz, 4JHH = 1.6 Hz, 0.83H, Ar-
= 8.1 Hz, 0.5H, Ar-H), 7.50 (d, JHH = 8.5 Hz, 0.5H, Ar-H), 7.32 (d,
3JHH = 8.3 Hz, 0.5H, Ar-H), 7.28−7.21 (m, 1H, Ar-H), 7.21−7.11 (m,
3H, Ar-H), 7.06 (d, 3JHH = 8.3 Hz, 0.5H, Ar-H), 7.04−7.01 (m, 0.5H,
Ar-H), 6.93 (s, 2H, Ar-H), 6.76 (t, 3JHH = 7.3 Hz, 1H), 6.59−6.56 (m,
1H, Ar-H), 6.35 (s, 2H, Ar-H), 5.34 (hept, 3JHH = 6.6 Hz, 0.5H, down-
3
H), 7.71 (d, JHH = 8.2 Hz, 0.26H, Ar-H), 7.69−7.66 (m, 0.27H, Ar-
3
H), 7.64−7.60 (m, 1H, Ar-H), 7.59 (d, JHH = 6.0 Hz, 0.85H, Ar-H),
3
7.56−7.49 (m, 2H, Ar-H), 7.38 (d, JHH = 8.6 Hz, 0.28H, Ar-H),
3
7.34−7.18 (m, 4H, Ar-H), 7.16 (d, JHH = 8.4 Hz, 0.83H, Ar-H),
3
methine), 5.26 (hept, JHH = 6.5 Hz, 0.5H, up-methine), 3.92 (s, 4H,
7.06−6.89 (m, 2H, Ar-H), 6.82−6.71 (m, 1H, Ar-H), 6.59 (dd, 3JHH
=
=
4
3
4
NHC-methylenes), 2.54 (s(br), 8H, Ar-methyl), 2.22−2.08 (m, 8H,
Ar-methyl), 1.66 (dd, J = 22.9 Hz, 3JHH = 6.5 Hz, 3H, iPr-methyl), 1.50
(dd, J = 24.6 Hz, 3JHH = 6.5 Hz, 3H, iPr-methyl). 13C{1H} NMR (101
MHz, THF-d8): δ 249.38, 248.47, 220.63, 220.37, 155.67, 152.30,
150.00, 143.07, 139.82, 138.64, 137.68, 137.32, 136.48, 134.71, 131.57,
131.48, 130.57, 130.03, 129.21, 129.07, 128.95, 128.50, 128.31, 128.02,
127.45, 127.36, 125.32, 125.10, 125.07, 124.89, 124.83, 124.78, 123.63,
122.84, 122.75, 122.04, 120.73, 116.27, 116.20, 81.63, 81.57, 52.25,
24.32, 24.20, 22.11, 22.06, 21.22, 19.81, 18.09. HRMS (FAB+): [M]+
C41H44N2OS2Ru calculated 746.1939, found 746.1932.
7.5 Hz, JHH = 1.7 Hz, 0.72H, Ar-H), 6.55 (dd, JHH = 7.5 Hz, JHH
3
1.6 Hz, 0.28H, Ar-H), 6.25 (s, 1H, Ar-H), 5.43 (hept, JHH = 6.6 Hz,
3
0.3H, down-methine), 5.19 (hept, JHH = 6.5 Hz, 0.83H, up-methine),
4.07−3.85 (m, 4H, NHC-methylenes), 2.94 (s, 2H, Ar-methyl), 2.73−
2.34 (m, 4H, Ar-methyl), 2.14 (d, J = 57.4 Hz, 10H, Ar-methyl), 1.77
(d, 3JHH = 6.5 Hz, 1H, Ar-methyl), 1.62−1.59 (m, 4H, Ar-methyl, iPr-
methyl), 1.47 (d, 3JHH = 6.4 Hz, 3H, iPr-methyl). 13C{1H} NMR (101
MHz, CDCl3): δ 248.94, 248.61, 220.27, 220.06, 157.07, 155.71,
155.52, 151.58, 143.90, 143.01, 142.96, 139.15, 138.67, 137.85, 137.30,
136.99, 136.52, 134.51, 134.38, 133.40, 132.58, 131.44, 131.20, 131.07,
130.63, 130.56, 130.27, 130.00, 129.56, 129.19, 128.98, 128.95, 128.48,
128.29, 128.15, 128.11, 127.54, 127.46, 125.46, 125.37, 125.33, 125.14,
125.00, 124.32, 124.18, 124.08, 123.48, 122.90, 122.81, 122.39, 116.31,
116.05, 81.67, 80.92, 52.29, 52.24, 24.35, 24.09, 22.26, 22.17, 21.25,
Ruthenium Catalyst III. This compound was synthesized according
to the representative procedure; the reaction was conducted on a 0.29
mmol scale. Ruthenium catalyst III was formed as a brown solid (180
1
mg, 80% yield) and mixture of isomers. H NMR (400 MHz, THF-
L
Organometallics XXXX, XXX, XXX−XXX