1732 Organometallics, Vol. 21, No. 8, 2002
Nelson et al.
Ta ble 4. Selected Bon d Dista n ces (Å) a n d Bon d
An gles (d eg) for 1b, 3b, 5b, a n d 6b
Ta ble 5. Ru (II/III) P oten tia ls for 1a -7a , 1b-3b, 5b,
6b, 1c, a n d 4c
1b
3b
5b
3b
E1/2
Ru(II/III)
(V)a
E1/2
Ru(II/III)
(V)a
∆Ep
∆Ep
(mV)
Ru-As
2.4630(6)) 2.4649(5) 2.4834(3) 2.4713(3)
compound
(mV) compound
Ru-Cl(1)
2.429(1)
2.391(1)
2.187(4)
85.84(3)
86.04(3)
2.436(2)
2.392(2)
2.200(7)
86.11(5)
85.65(5)
87.66(8)
2.4242(7) 2.4166(7)
2.4117(3) 2.4021(7)
2.198(3)
84.47(3)
88.70(2)
87.61(3)
Ru-Cl(2)
1a
2a
3a
4a
5a
6a
7a
0.76
0.70
0.71
0.66
0.70
0.61
0.48
152
122
272
161
174
150
126
1b
2b
3b
5b
6b
1c
4c
0.67
0.60
0.60
0.60
0.51
0.77
0.65
83
145
112
94
133
153
158
Ru-(C1-C6)a
As-Ru-Cl(1)
As-Ru-Cl(2)
2.206(30
84.92(2)
82.74(2)
88.09(2)
Cl(1)-Ru-Cl(2) 86.06(4)
a
(C1-C6) denotes the average Ru-C distances.
a
Measured at 298 K in CH2Cl2 solutions at a glassy carbon
working electrode, 0.1 M tetrabutylammonium hexafluorophos-
phate as supporting electrolyte. All potentials are vs Fc/Fc+. Scan
rate 100 mV/s.
4a : mp 211-213 °C (90% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C ): δ 7.71 (m, 4H, Ho), 7.40 (m, 6H, Hm,p), 6.80
3
(dd, 3J (HaHc) ) 18.5 Hz, J (HaHb) ) 11.5 Hz, 1H, Ha), 5.98 (d,
3
3J (HaHb) ) 11.5 Hz, 1H, Hb), 5.47 (d, J (HaHc) ) 18.5 Hz, 1H,
Hc), 4.82 (s, 3H, CH, arene), 1.99 (s, 9H, 3CH3). 13C{1H} NMR
(125.7 MHz, CDCl3, 25 °C): δ 133.41 (Co), 132.66 (Câ), 132.30
(CR), 129.98 (Cp), 129.10 (Ci), 128.48 (Cm), 101.62 (Cq, arene),
81.72 (CH, arene), 18.63 (CH3). Anal. Calcd for C23H25AsCl2-
Ru: C, 50.40; H, 4.56; Cl, 12.94. Found: C, 50.26; H, 4.39; Cl,
12.68.
2b: mp 219-221 °C (85% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 6.31 (dd, 3J (HaHc) ) 19.0 Hz, 3J (HaHb) ) 12.0
Hz, 1H, Ha), 5.85 (d, 3J (HaHb) ) 12.0 Hz, 1H, Hb), 5.57 (d,
3J (HaHc) ) 19.0 Hz, 1H, Hc), 5.34 (s, 4H, arene), 2.28 (t, 3J (HH)
2
) 12.0 Hz, 2H HRa) 1.95 (s, 6H, CH3), 1.90 (d, J (HH) ) 13.0
Hz, 2H, Hâe), 1.80 (d, 2J (HH) ) 13.0 Hz, 2H, Hâe), 1.65 (d,
5a : mp 186-189 °C (95% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 7.68 (m, 4H, Ho,), 7.40 (m, 6H, Hm,p), 6.91
2
2J (HH) ) 13.0 Hz, 2H, Hγ e), 1.62 (d, J (HH) ) 13.0 Hz, 2H,
Hγe), 1.54 (d, 3J (HH) ) 10.0 Hz, 2H, Hδ), 1.32 (dt, 2J (HH) )
3
(dd, 3J (HaHc) ) 18.5 Hz, J (HaHb) ) 11.4 Hz, 1H, Ha), 5.98 (d,
3
2
13.0 Hz, J (HH) ) 12.0 Hz, 2H, Hâa), 1.29 (dt, J (HH) ) 13.0
Hz, 3J (HH) ) 12.0 Hz, 2H, Hâa), 1.07 (m, 6H, Hγδ). 13C{1H}
NMR (125.7 MHz, CDCl3, 25 °C): δ 128.97 (CR), 127.77 (Câ),
93.42 (Cq, arene), 84.87 (CH, arene), 36.74 (CR′), 28.70 (Câ′),
28.34 (Câ′), 26.66 (Cγ′), 26.50 (Cγ′), 25.32 (Cδ′), 17.24 (2CH3).
Anal. Calcd for C22H35AsCl2Ru: C, 48.38; H, 6.41; Cl, 12.98.
Found: C, 48.12; H, 6.19; Cl, 12.73.
3
3J (HaHb) ) 11.4 Hz, 1H, Hb), 5.43 (d, J (HaHc) ) 18.5 Hz, 1H,
Hc), 5.28, 5.30 (AB, 3J (HH) ) 6.0 Hz, 4H, CH, arene), 2.63
3
(septet, J (HH) ) 6.9 Hz, 1H, CH), 1.91 (s, 3H, CH3), 0.96 (d,
3J (HH) ) 6.9 Hz, 6H, 2CH3). 13C{1H} NMR (125.7 MHz, CDCl3,
25 °C): δ 133.88 (Câ), 133.15 (Co), 131.14 (CR) 130.03 (Cp),
128.57 (Cm) Ci not observed, 106.84, 95.19, 85.62, 83.25 (C,
arene), 38.26 (CH, arene), 21.48 (2CH3), 17.69 (CH3). Anal.
Calcd for C24H27AsCl2Ru: C, 51.28; H, 4.80; Cl, 12.61. Found:
C, 51.41; H, 4.98; Cl, 12.52.
3b: mp 210-200 °C (87% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 6.38 (dd, 3J (HaHc) ) 19.0 Hz, 3J (HaHb) ) 12.0
Hz, 1H, Ha), 5.94 (d, 3J (HaHc) ) 12.0 Hz, 1H, Hc), 5.67 (d,
3J (HaHc) ) 19.0 Hz, 1H, Hb), 5.27 (m, [AX]2, 2H, arene), 5.16
(m, [AX]2, 2H arene) 2.36 (tt, 3J (HH) ) 12.5, 3J (HH) ) 12.5
6a : mp 199-200 °C (85% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 7.71 (m, 4H, Ho), 7.39 (m, 6H, Hm,p), 6.90
3
(dd, 3J (HaHc) ) 18.3 Hz, J (HaHb) ) 11.3 Hz, 1H, Ha), 5.93 (d,
2
Hz, 2H, HRa), 2.05 (s, 6H, 2CH3), 1.95 (d, J (HH) ) 13.0 Hz,
3
3J (HaHb) ) 11.3 Hz, 1H, Hb), 5.46 (d, J (HaHc) ) 18.3 Hz, 1H,
2
2
2H, Hâe), 1.89 (d, J (HH) ) 13.0 Hz, 2H Hâe), 1.77 (d, J (HH)
Hc), 4.98 (s, 2H, arene) 1.82 (s, 12H, 4CH3). 13C{1H} NMR
(125.7 MHz, CDCl3, 25 °C): δ 132.74 (Co), 132.42 (Câ), 131.92
(CR), 129.38 (Cp), 128.59 (Ci), 127.91 (Cm), 94.49 (Cq, arene),
87.49 (CH, arene), 15.64 (CH3). Anal. Calcd for C24H27AsCl2-
Ru: C, 51.28; H, 4.80; Cl, 12.61. Found: C, 51.14; H, 4.63; Cl,
12.49.
2
3
) 19.5 Hz, Hγ), 1.71 (t, J (HH) ) J (HH) ) 12.5 Hz, 2H, Hδ),
1.61 (d, 2J (HH) ) 11.0 Hz, 2H, Hδ), 1.39 (apparent qd, 2J (HH)
) 3J (HH) ) 12.5 Hz,3J (HH) ) 2.5 Hz, 2H, Hâa), 1.36 (apparent
qd, 2J (HH) ) 3J (HH) ) 12.5 Hz,3J (HH) ) 2.5 Hz, 2H, Hâa),
1.15 (m, 6H, 4Hγ , 2Hδ). 13C{1H} NMR (125.7 MHz, CDCl3, 25
°C): δ 130.06 (CR), 128.81 (Câ), 101.29 (Ci, arene), 85.23 (CH,
arene), 77.40 (CH, arene), 37.47 (CR′), 29.32 (Câ′), 29.15 (Câ′),
27.25 (Cγ′′), 27.08 (Cγ′′), 25.84 (Cδ′), 16.26 (2CH3). Anal. Calcd
for C22H35AsCl2Ru: C,48.38; H, 6.41; Cl, 12.98. Found: C,
48.14; H, 6.29; Cl, 12.82.
7a : mp > 200 dec (92% yield). 1H NMR (500.0 MHz, CDCl3,
25 °C): δ 7.73 (m, 4H, Ho), 7.41 (m, 6H, Hm,p), 6.89 (dd,
3J (HaHc) ) 18.5 Hz, 3J (HaHb) ) 11.5 Hz, 1H, Ha), 5.92 (d,
3
3J (HaHb) ) 11.5 Hz, 1H, Hb), 5.47 (d, J (HaHc) ) 18.5 Hz, 1H,
Hc), 1.85 (s, 18H, 6CH3). 13C{1H} NMR (125.7 MHz, CDCl3,
25 °C): δ 134.10 (Co), 133.99 (CR), 132.34 (Câ), 129.86 (Cp),
128.42 (Cm), 128.07 (Ci), 93.90 (C, arene), 15.49 (CH3, arene).
Anal. Calcd for C26H31AsCl2Ru: C, 52.91; H, 5.25; Cl, 12.01.
Found: C, 52.69; H, 5.31; Cl, 11.94.
5b: mp 173-176 °C (88% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 6.37 (dd, 3J (HaHc) ) 19.0 Hz, 3J (HaHb) ) 12.0
Hz, 1H, Ha), 5.95 (d, 3J (HaHb) ) 12.0 Hz, 1H, Hb), 5.65 (d,
3
3J (HaHc) ) 19.0 Hz, 1H, Hc), 5.40, 5.38 (AB, J (HH) ) 6.0 Hz,
4H, ring), 2.79 (sept, 3J (HH) ) 7.0 Hz, 1H, CH) 2.37 (t, 3J (HH)
2
1b: mp 177-179 °C (95% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 6.31 (dd, 3J (HaHc) ) 19.0 Hz, 3J (HaHb) ) 12.0
Hz, 1H, Ha), 5.87 (d, 3J (HaHb) ) 12.0 Hz, 1H, Hb), 5.60 (d,
3J (HaHc) ) 19.0 Hz, 1H, Hc), 5.50 (apparent t, 3J (HH) ) 5.0
) 12.5 Hz, 2H, HRa) 2.02 (s, 3H, CH3) 1.95 (d, J (HH) ) 12.5
Hz, 2H, Hâe), 1.87 (d, 2J (HH) ) 12.5 Hz, 2H, Hâe), 1.68 (m,
4H, Hγ ), 1.59 (m, 4H, Hδ), 1.43 (apparent quart., 3J (HH) )
3
12.5 Hz, 2H, Hâa), 1.36 (aparent q, 2J (HH) ) J (HH) ) 12.5
Hz, 2H, Hâa), 1.15 (d, 3J (HH) ) 7.0 Hz, 6H, CH3), 1.14 (m, 6H,
3
3
Hz, 2H, Hm), 5.22 (d, J (HH) ) 5.0 Hz, 2H Ho) 5.16 (t, J (HH)
) 5.0 Hz, 1H, Hp), 2.31 (t, 3J (HH) ) 12.5 Hz, 2H, HRa), 2.09 (s,
3H, CH3), 1.90 (d, 2J (HH) ) 11.5 Hz, 2H, Hâe), 1.82 (d, 2J (HH)
H
γδ). 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C): δ 129.53 (CR),
128.14 (Câ), 105.89 (Cq, arene), 93.69 (Cq, arene), 84.95 (CH,
arene), 81.60 (CH, arene), 36.97 (CR′), 29.84 (CH), 29.02 (Câ′),
28.54 (Câ′), 27.06 (Cγ′), 26.92 (Cγ′), 25.62 (Cδ′), 21.58 (2CH3),
17.66 (CH3). Anal. Calcd for C24H39AsCl2Ru: C, 50.16; H, 6.79;
Cl, 12.35. Found: C, 49.93; H, 6.60; Cl, 12.21.
6b: mp 198-200 °C (93% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 6.40 (dd, 3J (HaHc) ) 19.0 Hz, 3J (HaHb) ) 12.0
Hz, 1H, Ha), 5.95 (d, 3J (HaHb) ) 12.0 Hz, 1H, Hb), 5.65 (d,
3J (HaHc) ) 19.0 Hz, 1H, Hc), 5.25 (s, 2H, arene H), 2.37 (tt,
3J (HH) ) 12.5 Hz, 3J (HH) ) 3.0 Hz, 2H HRa) 1.97 (s, 12H CH3),
1.96 (d, 2J (HH) ) 12.5 Hz, 2H, Hâe), 1.87 (d, 2J (HH) ) 12.5
2
) 12.5 Hz, 2H Hâe), 1.67 (d, J (HH) ) 11.5 Hz, 2H, Hγ e), 1.62
2
3
(d, J (HH) ) 11.0 Hz, 2H, Hγe), 1.54 (d, J (HH) ) 9.5 Hz, 2H,
Hδ), 1.33 (q 2J (HH) ) 3J (HH) ) 12.5 Hz, 2H, Hâa), 1.30 (q,
2J (HH) ) 3J (HH) ) 12.5 Hz, 2H, Hâa), 1.10 (m, 6H, Hγδ).
13C{1H} NMR (125.7 MHz, CDCl3, 25 °C): δ 129.29 (CR), 128.48
(Câ), 105.16 (Ci, arene), 84.24 (Co, arene), 84.20 (Cm, arene),
74.73 (Cp, arene), 32.28 (CR′), 29.94 (Câ′), 28.83 (Câ′), 26.92 (Cγ′′)
26.74 (Cγ′′), 25.48 (Cδ′), 18.04 (CH3). Anal. Calcd for C22H35
-
AsCl2Ru: C, 47.40; H, 6.20; Cl, 13.32. Found: C, 47.16; H, 6.27;
Cl, 13.09.