Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
1027 (m), 999 (w), 970 (w), 951 (w), 939 (vw), 911 (br vw), 867 (sh),
699 (s), 691 (s), 674 (m), 627 (vw), 620 (w), 610 (w), 601 (vw), 596
846 (m), 804 (br m), 739 (vs), 695 (vs), 670 (sh), 652 (m), 619 (sh),
(vw), 592 (vw), 586 (vw), 579 (vw), 574 (vw), 567 (vw), 546 (vw), 540
(vw), 537 (vw), 521 (sh), 515 (s), 502 (s), 489 (m), 477 (m), 461 (br w),
442 (vw), 411 (m), 406 (br m), 375 (vw), 364 (vw), 352 (vw), 336 (w),
328 (vw), 323 (vw), 314 (vw), 312 (vw), 305 (vw), 301 (vw), 290 (vw),
286 (vw), 282 (vw), 272 (br vw), 261 (vw), 253 (vw), 250 (sh), 245
(vw), 239 (vw), 234 (vw), 230 (vw), 225 (sh), 220 (m), 212 (sh), 208
(s), 203 (s), 192 (br s), 183 (sh), 178 (w), 173 (vw), 169 (m), 166 (m),
161 (m), 157 (m), 155 (sh), 147 (sh), 145 (m), 142 (m), 136 (m), 131
(m), 126 (w), 116 (br s), 110 (s), 106 (m), 102 (m), 97 (sh), 95 (s), 89
513 (m), 482 (m), 452 (vw), 422 (w) cmÀ 1
.
Synthesis of trpd-3pln
To a solution of lithium phospholanide (194 mg, 2.06 mmol) in THF
(20 mL) a solution of n-butyllithium in n-hexane (2.5 m, 0.14 mL,
°
0.35 mmol) was added at 0 C. to this solution. The ligand precursor
1,3-Dichloro-2-(chloromethyl)-2-methylpropane (117 mg, 667 μmol)
(s), 85 (m) cmÀ 1
.
°
was added to this solution at 0 C. The solution was stirred for 4 d
at room temperature. The solvent was removed in vacuo. The
residue was redissolved in n-pentane (10 mL), filtered over Celite®
and washed with n-pentane (30 mL). The solvent was removed in
vacuo. After redissolving the oily residue in diethyl ether (5 mL)
degassed water (5 mL) was added and it was stirred for 5 min. The
solvent of the separated organic layer was removed in vacuo. The
oily residue was redissolved in dichloromethane (5 mL), filtered
over basic aluminum oxide and washed with dichloromethane
(30 mL). After removing the solvent in vacuo the product was
obtained as colorless oil (213 mg). The formation of trpd-3pln was
accompanied by side reactions and not all side products, which
were probably caused by a lithium halogen exchange, could be
separated and identified. So that the yield of trpd-3pln could not
be determined. Therefore, a small excess of the product was used
for the synthesis of [MoBr3(trpd-3pln)] (3).
[MoI3(trpd-2pln)] (2)
The ligand trpd-2pln (128 mg, 299 μmol) was dissolved in THF
(5 mL). This solution was added to a suspension of [MoI3(thf)3]
(200 mg, 289 μmol) and THF (15 mL). It was stirred for 42 h at room
temperature. The suspension was reduced in vacuo to a quantity of
5 mL and diethyl ether (20 mL) was added. The precipitate was
filtered, washed with diethyl ether (15 mL) and dried in vacuo. The
product was obtained as red-brown solid (159 mg, 299 μmol, 61%).
Anal. Calcd C25H35I3MoP3 (905.15): C 33.2, H 3.9, IÀ 42.1; C 33.0, H
4.0, IÀ 40.6.
~
MIR-FIR: n=3077 (sh), 3052 (w), 2970 (sh), 2936 (m), 2865 (m), 2658
(vw), 2115 (vw), 2080 (vw), 2051 (vw), 1981 (vw), 1939 (w), 1875 (w),
1825 (sh), 1809 (br w), 1636 (sh), 1616 (sh), 1587 (w), 1573 (w), 1480
(w), 1457 (w), 1435 (s), 1406 (m), 1378 (m), 1337 (w), 1317 (sh), 1303
(w), 1279 (vw), 1253 (w), 1182 (w), 1150 (w), 1139 (sh), 1113 (s),
1094 (sh), 1067 (s), 1028 (m), 999 (w), 974 (sh), 952 (br m), 912 (w),
877 (sh), 856 (s), 836 (sh), 824 (sh), 794 (sh), 740 (br s), 720 (vw), 694
(br s), 664 (sh), 617 (vw), 605 (vw), 574 (w), 553 (m), 513 (s), 498 (s),
428 (br m), 398 (sh), 313 (vw), 303 (vw), 273 (vw), 260 (vw), 248 (sh),
204 (s), 182 (sh), 160 (m), 156 (m), 145 (m), 136 (m), 127 (m), 111
31P{1H} NMR: (161.98 MHz, CDCl3, 300 K): δ=À 36.5 (s, 3 P, Ppln) ppm.
1H-NMR (400.13 MHz, CDCl3, 300 K): δ=1.83–1.59 (2 m, 22 H, CH2
(pln)), 1.64 (br d, 6 H, CqÀ CH2À Ppln), 1.54–1.46 (m, 7 H, CH2 (pln)),
1.07 (s, 3 H, CH3) ppm.
1
13C{1H}-NMR (101 MHz, CDCl3, 300 K): δ=44.0–43.6 (dt, JPC
=
3
2
20.9 Hz, JCP =8.3 Hz, 3 C, CqÀ CH2À Ppln), 37.2–36.8 (q, JCP =11.8 Hz,
1 C, CqÀ CH3), 27.7–27.4 (q, 3JCP =8.9 Hz, 1 C, CH3), 27.0–26.9 (m, 12 C,
CH2 (pln)) ppm.
(m), 98 (m), 93 (vw), 87 (m), 83 (sh) cmÀ 1
.
IR (ATR): v˜=2949 (sh), 2928 (s), 2875 (sh), 2857 (s), 1666 (w), 1640
(w), 1616 (w), 1603 (w), 1460 (s), 1445 (s), 1422 (s), 1405 (s), 1365 (s),
1315 (w), 1300 (m), 1259 (br s), 1203 (m), 1189 (sh), 1166 (s), 1110
(s), 1075 (s), 1049 (s), 1027 (s), 1008 (sh), 974 (w), 952 (w), 917 (w),
875 (sh), 861 (sh), 847 (s), 808 (br s), 792 (br s), 773 (sh), 727 (br m),
720 (br m), 680 (sh), 665 (m), 649 (s), 545 (sh), 512 (br s), 474 (br s)
[MoBr3(trpd-3pln)] (3)
The ligand trpd-3pln (207 mg, 627 μmol) was dissolved in THF
(15 mL). This solution was added to [MoBr3(thf)3] (300 mg,
543 μmol) and it was stirred for 18 h at room temperature. The
suspension was reduced in vacuo to a quantity of 5 mL and diethyl
ether (20 mL) was added. The precipitate was filtered, washed with
diethyl ether (20 mL), n-hexane (10 mL) and again with diethyl
ether (10 mL) and dried in vacuo. The product was obtained as
yellow solid (258 mg, 387 μmol, 71%).
cmÀ 1
.
[MoI3(trpd-1pln)] (1)
The ligand trpd-3pln (105 mg, 199 μmol) was dissolved in THF
(10 mL). This solution was added to a suspension of [MoI3(thf)3]
(135 mg, 195 μmol) and THF (5 mL). It was stirred for 62 h at room
temperature. The suspension was reduced in vacuo to a quantity of
6 mL and diethyl ether (15 mL) was added. The precipitate was
filtered, washed with diethyl ether (15 mL) and n-hexane (15 mL)
and dried in vacuo. The product was obtained as red-brown solid
(117 mg, 117 μmol, 60%).
Anal. Calcd C17H33Br3MoP3 (666.04): C 30.7, H 5.0, BrÀ 36.0; found C
31.2, H 5.0, BrÀ 35.6.
~
MIR-FIR: n=2978 (sh), 2936 (m), 2865 (m), 1473 (sh), 1464 (sh),
1457 (m), 1446 (m), 1437 (sh), 1419 (sh), 1406 (br m), 1399 (sh),
1388 (vw), 1380 (m), 1363 (sh), 1339(vw), 1320 (vw), 1304 (w), 1262
(br w), 1225 (vw), 1203 (sh), 1180 (w), 1111 (s), 1061 (s), 1029 (m),
950 (m), 914 (vw), 875 (sh), 857 (s), 821 (sh), 791 (vw), 764 (vw), 747
(vw), 717 (w), 675 (m), 543 (sh), 512 (m), 495 (s), 462 (sh), 280 (vw),
252 (sh), 245 (sh), 234 (vs), 228 (sh), 214 (vw), 209 (vw), 203 (w), 197
(vw), 193 (vw), 188 (vw), 182 (vw), 177 (w), 170 (w), 163 (sh), 158 (s),
152 (m), 146 (sh), 140 (w), 132 (w), 127 (vw), 122 (w), 110 (w), 105
Anal. Calcd C33H37I3MoP3 (1003.25): C 39.5, H 3.7, IÀ 38.0; found C
39.3, H 4.1, IÀ 38.1.
~
MIR-FIR: n=3078 (vw), 3055 (vw), 3029 (vw), 2974 (sh), 2955 (w),
(w), 99 (m), 95 (w), 91 (sh), 85 (br m), 80 (m) cmÀ 1
.
2932 (w), 2918 (w), 2857 (br w), 1586 (w), 1574 (w), 1483 (m), 1458
(vw), 1448 (w), 1433 (s), 1416 (w), 1413 (sh), 1402 (w), 1375 (w),
1364 (vw), 1336 (w), 1318 (w), 1305 (w), 1277 (w), 1267 (sh), 1256
(sh), 1234 (sh), 1223 (w), 1212 (vw), 1189 (w), 1158 (w), 1139 (w),
1115 (m), 1089 (br m), 1080 (vw), 1066 (m), 1048 (w), 1027 (w), 999
(w), 985 (vw), 953 (vw), 934 (vw), 914 (br w), 905 (br w), 876 (w), 854
(m), 835 (m), 815 (w), 777 (vw), 769 (vw), 752 (m), 743 (s), 723 (m),
[Mo(N2)(trpd-3pln)(dppm)] (4)
[MoBr3(trpd-3pln)] (3, 320 mg, 480 μmol) and the coligand dppm
(185 mg, 481 μmol) was added to sodium amalgam (200 mg,
Z. Anorg. Allg. Chem. 2021, 1–12
9
© 2021 The Authors. Zeitschrift für anorganische und allgemeine Chemie
published by Wiley-VCH GmbH.
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