Organometallics
Article
(m), 659 (m), 640 (w), 611 (m), 602 (m), 573 (m). MS (CI+,
isobutane): 679 [B(C6F5)4]+, 512 [B(C6F5)3]+, 334 [C6F5−C6F5]+,
168 [C6F5H]+, 107 [Ag]+, 107 [C8H10+H]+, 106 [C8H10]+.
1296 (w), 1274 (m), 1191 (w), 1082 (s), 1035 (m), 995 (m), 974
(s), 926 (m), 893 (m), 848 (m), 774 (m), 769 (m), 755 (m), 726
(m), 694 (m), 683 (m), 660 (m), 610 (m), 602 (m), 573 (m). MS
(CI+, isobutane): 1100 [Ag4(C6F5)4]+, 933 [Ag4(C6F5)3]+, 513
[B(C6F5)3 + H]+, 512 [B(C6F5)3]+, 345 [C6F5−B−C6F5] +, 334
[C6F5−C6F5]+, 168 [C6F5H]+, 227 [C9H12Ag]+, 121 [C9H12 + H]+,
120 [C9H12]+, 119 [C9H11]+, 107 [Ag]+, 105 [C8H9]+, 91 [C7H7]+.
arene = 1,3,5-Triisopropylbenzene, [Ag(C15H24)3][B(C6F5)4]. Mp
117 °C. Anal. Calcd (for [Ag(C15H24)2][B(C6F5)4]) (found): C,
arene = 1,2,3-Trimethylbenzene, [Ag(C9H12)3][B(C6F5)4]. Mp 148
°C dec. Anal. Calcd (for [Ag(C9H12)3][B(C6F5)4]) (found): C, 53.38
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(52.69); H, 3.16 (3.20). H NMR (25 °C, CD2Cl2, 300.13 MHz): δ
2.22 (s, 3H, ArCH3), 2.30 (s, 6H, ArCH3), 6.87 (t, 1H, 1J(1H−13C) =
6.99 Hz), ArCH), 6.96 (d, 1H, 1J(1H−13C) = 6.99 Hz), 6.98 (d, 1H,
1J(1H−13C) = 6.99 Hz). 11B NMR (25 °C, CD2Cl2, 96.3 MHz): δ
−16.63. 13C{1H} NMR (25 °C, CD2Cl2, 62.89 MHz): δ 16.0 (s, CH3,
1,2,3-trimethylbenzene), 21.0 (s, 2CH3, 1,2,3-trimethylbenzene),
118.5 (s, CH, 1,2,3-trimethylbenzene), 124.5 (s, 2CH, 1,2,3-
trimethylbenzene), 124.8 (br, ipso-C), 137.0 (dm, m-CF,
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54.25 (52.74); H, 4.05 (4.28). H NMR (25 °C, CD2Cl2, 300.13
MHz): δ 1.22 (s, 9H, 3CH3), 1.24 (s, 9H, 3CH3), 2.89 (sept, 3H, CH,
3J(1H−1H) = 6.8 Hz), 7.02 (s, 3H, ArCH). 11B NMR (25 °C,
CD2Cl2, 96.3 MHz): δ −16.62. 13C{1H} NMR (25 °C, CD2Cl2, 62.89
MHz): δ 24.7 (s, 6CH3, 1,3,5-triisopropylbenzene), 34.9 (s, 3CH,
1,3,5-triisopropylbenzene), 119.6 (s, 3CH, 1,3,5-triisopropylbenzene),
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1J(13C−19F) = 245 Hz), 138.8 (dm, p-CF, J(13C−19F) = 243 Hz),
139.6 (s, C, 1,2,3-trimethylbenzene),140.3 (s, 2C, 1,2,3-trimethylben-
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124.1 (br, ipso-C), 136.9 (dm, m-CF, J(13C−19F) = 247 Hz), 138.8
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zene), 148.70 (dm, o-CF, J(13C−19F) = 245 Hz).19F{1H} NMR (25
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(dm, p-CF, J(13C−19F) = 245 Hz), 148.7 (dm, o-CF, J(13C−19F) =
244 Hz), 152.6 (s, 3C, 1,3,5-triisopropylbenzene).19F{1H} NMR (25
°C, CD2Cl2, 282.4 MHz): −167.6 (m, m-CF, 1J(13C−19F) = 245 Hz),
−163.8 (dm, p-CF, 1J(13C−19F) = 245 Hz), −133.0 (dm, o-CF,
1J(13C−19F) = 241 Hz). IR (ATR, 16 scans, cm−1): 2966 (m), 2929
(m), 2873 (w), 1642 (m), 1588 (w), 1574 (w), 1557 (w), 1511 (m),
1456 (s), 1412 (m), 1384 (m), 1367 (m), 1316 (w), 1274 (m), 1187
(w), 1083 (s), 1033 (w), 975 (s), 927 (m), 904 (m), 881 (m), 829
(w), 792 (w), 773 (m), 770 (m), 755 (m), 725 (m), 683 (m), 660
(m), 610 (m), 602 (m), 573 (m). MS (CI+, isobutane): 513
[B(C6F5)3 + H]+, 334 [C6F5−C6F5]+, 243 [C15H24 + C3H3]+, 205
[C15H24 + H]+, 204 [C15H24]+, 203 [C15H23]+, 163 [C12H18 + H]+.
arene = 1,2,3,5-Tetramethylbenzene, [Ag(C10H14)3][B(C6F5)4]. Mp
184 °C. Anal. Calcd (for [Ag(C10H14)3][B(C6F5)4]) (found): C,
°C, CD2Cl2, 282.4 MHz): −167.5 (m, m-CF, 1J(13C−19F) = 245 Hz),
−163.7 (dm, p-CF, 1J(13C−19F) = 243 Hz), −133.0 (dm, o-CF,
1J(13C−19F) = 245 Hz). IR (ATR, 16 scans, cm−1): 2984 (w), 2917
(w), 2867 (w), 1644 (m), 1585 (w), 1573 (w), 1537 (w), 1514 (s),
1460 (s), 1456 (s), 1412 (m), 1383 (m), 1274 (m), 1245 (m), 1160
(w), 1083 (s), 1035 (w), 976 (s), 899 (w), 791 (s), 775 (s), 756 (s),
725 (w), 710 (w), 684 (m), 660 (s), 610 (m), 602 (m), 573 (m), 533
(w). MS (CI+, isobutane): 1100 [Ag4(C6F5)4]+, 933 [Ag4(C6F5)3]+,
513 [B(C6F5)3 + H]+, 512 [B(C6F5)3]+, 334 [C6F5−C6F5]+, 121
[C9H12 + H]+, 120 [C9H12]+, 119 [C9H11]+, 107 [Ag]+, 105 [C8H9]+.
ESI-TOF/MS: (for [B(C6F5)4]) Calc. 678.98095, measured
678.97834.
arene = 1,2,4-Trimethylbenzene, [Ag(C9H12)3][B(C6F5)4]. Mp 147
°C dec. Anal. Calcd (for [Ag(C9H12)3][B(C6F5)4]) (found): C, 53.38
(53.10); H, 3.16 (3.16).1H NMR (25 °C, CD2Cl2, 300.13 MHz): δ
2.23 (s, 3H, ArCH3), 2.27 (s, 3H, ArCH3), 2.28 (s, 3H, ArCH3), 6.83
(d, 1H, 3J(1H−1H) = 7.2 Hz), ArCH), 6.97 (d, 1H, 3J(1H−1H) = 7.2
Hz, ArCH), 7.09 (s, 1H, ArCH). 11B NMR (25 °C, CD2Cl2, 96.3
MHz): δ −15.99. 13C{1H} NMR (25 °C, CD2Cl2, 75.46 MHz): δ
19.6 (s, CH3, 1,2,4-trimethylbenzene), 20.1 (s, CH3, 1,2,4-
trimethylbenzene), 21.2 (s, CH, 1,2,4-trimethylbenzene), 121.2 (s,
CH, 1,2,4-trimethylbenzene), 124.8 (br, ipso-C), 125.4 (s, CH, 1,2,4-
trimethylbenzene), 131.5 (s, CH, 1,2,4-trimethylbenzene), 136.2 (s,
C, 1,2,4-trimethylbenzene), 136.9 (dm, m-CF, 1J(13C−19F) = 245
Hz), 137.7 (s, C, 1,2,4-trimethylbenzene), 138.8 (dm, p-CF,
1J(13C−19F) = 244 Hz), 140.0 (s, C, 1,2,4-trimethylbenzene), 148.7
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54.52 (54.01); H, 3.56 (3.68). H NMR (25 °C, CD2Cl2, 300.13
MHz): δ 2.16 (s, 3H, ArCH3), 2.22 (s, 3H, ArCH3), 2.26 (s, 6H,
2ArCH3), 6.82 (s, 2H, ArCH). 11B NMR (25 °C, CD2Cl2, 96.3
MHz): δ −16.65. 13C{1H} NMR (25 °C, CD2Cl2, 62.89 MHz): δ
15.5 (s, CH3, isodurene), 21.0 (s, 2CH3, isodurene), 21.2 (s, CH3,
isodurene), 123.3 (br, ipso-C), 125.1 (s, 2CH, isodurene), 134.7 (s, C,
isodurene), 135.6 (s, C, isodurene), 137.0 (dm, m-CF, 1J(13C−19F) =
1
245 Hz), 138.7 (dm, p-CF, J(13C−19F) = 245 Hz), 138.8 (s, 2C,
isodurene), 148.7 (dm, o-CF, 1J(13C−19F) = 241 Hz). 19F{1H} NMR
(25 °C, CD2Cl2, 282.4 MHz): −167.6 (m, m-CF, 1J(13C−19F) = 245
1
Hz), −163.7 (dm, p-CF, J(13C−19F) = 245 Hz), −133.1 (dm, o-CF,
1J(13C−19F) = 241 Hz). IR (ATR, 16 scans, cm−1): 2989 (w), 2952
(w), 2916 (w), 2863 (w), 1644 (m), 1599 (w), 1574 (w), 1564 (w),
1557 (w) 1538 (w), 1532 (w), 1513 (s), 1462 (s), 1412 (m), 1383
(m), 1277 (m), 1083 (s), 1037 (w), 977 (s), 926 (w), 908 (w), 891
(w), 863 (m), 775 (m), 768 (m), 756 (m), 726 (w), 709 (w), 684
(m), 661 (m), 610 (w), 602 (w), 573 (m), 556 (w), 546 (w), 521
(w), 475 (w), 449 (w), 416 (w), 409 (w). MS (CI+, isobutane): 513
[B(C6F5)3 + H]+, 512 [B(C6F5)3]+, 135 [C10H14 + H]+, 134
[C10H14]+, 133 [C10H13]+.
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(dm, o-CF, J(13C−19F) = 245 Hz). 19F{1H} NMR (25 °C, CD2Cl2,
282.4 MHz): −167.6 (m, m-CF, 1J(13C−19F) = 245 Hz), −163.7 (dm,
p-CF, 1J(13C−19F) = 244 Hz), −133.0 (dm, o-CF, 1J(13C−19F) = 245
Hz). IR (ATR, 16 scans, cm−1): 2977 (w), 2952 (w), 2929 (w), 2868
(w), 1644 (m), 1604 (w), 1558 (w), 1513 (s), 1461 (s), 1412 (m),
1388 (m), 1377 (m), 1274 (m), 1239 (m), 1204 (w), 1146 (m), 1083
(s), 1038 (w), 1025 (w), 977 (s), 907 (w), 890 (m), 847 (w), 832
(m), 775 (s), 769 (m), 756 (m), 725 (w), 714 (w), 704 (w), 683 (m),
660 (m), 627 (w), 609 (m), 602 (m), 573 (m), 545 (m). MS (CI+,
isobutane): 1100 [Ag4(C6F5)4]+, 933 [Ag4(C6F5)3]+, 513 [B(C6F5)3 +
H]+, 512 [B(C6F5)3]+, 345 [C6F5−B−C6F5] +, 334 [C6F5−C6F5]+,
168 [C6F5H]+, 127 [C9H12Ag]+, 121 [C9H12 + H]+, 120 [C9H12]+,
119 [C9H11]+, 107 [Ag]+, 105 [C8H9]+, 91 [C7H7]+.
arene = 1,2,4,5-Tetramethylbenzene, [Ag(C10H14)3][B(C6F5)4]. Mp
146 °C. Anal. Calcd (for [Ag(C10H14)3][B(C6F5)4]) (found): C,
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54.52 (54.29); H, 3.56 (3.40). H NMR (25 °C, CD2Cl2, 300.13
MHz): δ 2.20 (s, 12H, 4ArCH3), 6.93 (s, 2H, ArCH). 11B NMR (25
°C, CD2Cl2, 96.3 MHz): δ −16.64. 13C{1H} NMR (25 °C, CD2Cl2,
62.89 MHz): δ 19.6 (s, 4CH3, durene), 124.6 (br, ipso-C), 128.3 (s,
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2CH, durene), 135.6 (s, 4C, durene), 136.9 (dm, m-CF, J(13C−19F)
arene = 1,3,5-Trimethylbenzene, [Ag(C9H12)3][B(C6F5)4]. Mp 135
°C. Anal. Calcd (for [Ag(C9H12)2][B(C6F5)4]) (found): C, 49.11
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= 245 Hz), 138.8 (dm, p-CF, J(13C−19F) = 245 Hz), 148.7 (dm, o-
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1
CF, J(13C−19F) = 241 Hz). 19F{1H} NMR (25 °C, CD2Cl2, 282.4
(48.82); H, 2.35 (2.80). H NMR (25 °C, CD2Cl2, 300.13 MHz): δ
2.29 (s, 9H, ArCH3), 6.86 (m, 3H, ArCH). 11B NMR (25 °C, CD2Cl2,
96.3 MHz): δ −16.64. 13C{1H} NMR (25 °C, CD2Cl2, 75.47 MHz):
δ 21.6 (s, CH3, 1,3,5-trimethylbenzene), 124.1 (br, ipso-C), 125.6 (s,
1
MHz): −167.6 (m, m-CF, J(13C−19F) = 245 Hz), −163.7 (dm, p-
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CF, J(13C−19F) = 245 Hz), −133.0 (dm, o-CF, J(13C−19F) = 241
Hz). IR (ATR, 16 scans, cm−1): 2952 (w), 2926 (w), 2884 (w), 2866
(w), 1644 (m), 1605 (w), 1564 (w), 1555 (w), 1512 (s), 1495 (m),
1462 (s), 1413 (w), 1389 (m), 1277 (m), 1203 (w), 1083 (s), 1025
(m), 978 (s), 926 (w), 909 (w), 894 (m), 883 (m), 795 (w), 775 (m),
756 (m), 725 (w), 683 (m), 659 (m), 609 (m), 601 (m), 572 (m).
MS (CI+, isobutane): 512 [B(C6F5)3]+, 334 [C6F5−C6F5]+, 135
[C10H14 + H]+, 134 [C10H14]+, 133 [C10H13]+.
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3CH, 1,2,3-trimethylbenzene), 136.9 (dm, m-CF, J(13C−19F) = 245
1
Hz), 138.8 (dm, p-CF, J(13C−19F) = 245 Hz), 140.0 (s, 3C, 1,2,3-
trimethylbenzene), 148.7 (dm, o-CF, 1J(13C−19F) = 241 Hz).19F{1H}
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NMR (25 °C, CD2Cl2, 282.4 MHz): −167.5 (m, m-CF, J(13C−19F)
= 245 Hz), −163.6 (dm, p-CF, 1J(13C−19F) = 245 Hz), −133.2 (dm,
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o-CF, J(13C−19F) = 241 Hz). IR (ATR, 16 scans, cm−1): 2986 (w),
2952 (w), 2929 (w), 1643 (m), 1622 (w), 1602 (m), 1557 (w), 1538
(w) 1512 (s), 1456 (s), 1412 (m), 1383 (m), 1374 (m), 1326 (w),
arene = Pentamethylbenzene, [Ag(C11H16)3][B(C6F5)4]. Mp 171.31
°C. Anal. Calcd (for [Ag(C11H16)3][B(C6F5)4]·CH2Cl2) (found): C,
J
Organometallics XXXX, XXX, XXX−XXX