39:
227:
49:
363:
781:
illustrates an inherent difficulty in interpreting spectral data for new compounds: initial data may not provide reason to believe the structure deviates from a presumed geometry based on significant historical precedence, but there is always the possibility that the initial assignment will prove to
601:
symmetry including the hydrogen atoms. The structure (excluding the hydrogen atoms) can be thought of as consisting of a central atom, capped on either side by two eclipsing sets of three carbon atoms, with one triangular set slightly larger but also closer to the central atom than the other. The
754:
by opening up one set of three methyl groups (upper triangle) to wider C-W-C angles (94-97°) with slightly shorter C-W bond lengths, while closing the other set of three methyls (lower triangle) to 75-78° with longer bond lengths.
38:
424:, hexamethyltungsten is an air-sensitive, red, crystalline solid at room temperature; however, it is extremely volatile and sublimes at −30 °C. Owing to its six methyl groups it is extremely soluble in
376:
1516:
614:
results were interpreted in terms of an octahedral structure. In 1978, a study using photoelectron spectroscopy appeared to confirm the initial assignment of an
1645:
266:
1575:
1137:
Koutsospyros, A.; Braida, W.; Christodoulatos, C.; Dermatas D.; N. Strigul, N. (2006). "A review of tungsten: From environmental obscurity to scrutiny".
790:, yet new evidence and improved characterization methods suggested that perhaps there were exceptions to the rule, as evidenced by the case of W(CH
48:
1228:
Green, J. C.; Lloyd, D. R.; Galyer, L.; Mertis, K.; Wilkinson, G. (1978). "Photoelectron spectra of some transition metal alkyls and oxoalkyls".
762:. In 1995, before the work of Seppelt and Pfennig, Landis and coworkers had already predicted a distorted trigonal prismatic structure based on
1489:
1396:
1211:
1676:
1550:
1278:
Haalan, A.; Hammel, A.; Rydpal, K.; Volden, H. V. (1990). "The coordination geometry of gaseous hexamethyltungsten is not octahedral".
1023:
in 50% yield as an extremely volatile white solid. Hexamethyltungsten(VI) reacts with trimethylphosphine in light petroleum to give WMe
2164:
1585:
241:
1782:
1638:
421:
1251:
Morse, P. M.; Girolami, G. S. (1989). "Are d0 ML6 complexes always octahedral? The x-ray structure of trigonal-prismatic 2".
759:
2024:
2016:
787:
607:
477:
383:
2008:
116:
1940:
1921:
1631:
574:
205:
480:
methyl compound would prove to be more robust. In 1976, Wilkinson and Galyer disclosed an improved synthesis using
1172:
Galyer, A. L.; Wilkinson, G. (1976). "New synthesis of hexamethyltungsten(VI). The octamethyltungstate-(VI) lon".
2174:
2169:
1305:
Seppelt, K.; Pfennig, V. (1996). "Crystal and
Molecular Structures of Hexamethyltungsten and Hexamethylrhenium".
982:
2049:
1085:
670:
would also prove to be trigonal prismatic. This report prompted other investigations into the structure of W(CH
603:
1723:
1410:
Landis, C. K.; Cleveland, T.; Firman, T. K. (1995). "Making sense of the shapes of simple metal hydrides".
2096:
1862:
1838:
1766:
862:
1601:
Mertis, K.; Galyer, L.; Wilkinson, G. (1975). "Permethyls of tantalum, tungsten and rhenium: a warning".
42:
Stereo, skeletal formula of hexamethyltungsten with all implicit hydrogens shown, and assorted dimensions
1968:
1960:
1854:
1846:
1731:
1707:
1668:
1090:
993:
723:
635:
461:
429:
1531:
624:
The octahedral assignment remained for nearly 20 years until 1989 when
Girolami and Morse showed that
2121:
2080:
1952:
1909:
1822:
1774:
1314:
679:
441:
222:
2000:
1992:
1901:
1870:
1830:
1754:
1715:
1699:
763:
82:
1889:
1814:
1654:
1510:
1330:
587:
481:
453:
341:
825:. All are d complexes. Some 6-coordinate complexes with regular trigonal prismatic structures (D
1984:
1581:
1485:
1462:
1365:
1154:
730:
399:
156:
1976:
1809:
1610:
1554:
1546:
1454:
1419:
1392:
1357:
1322:
1287:
1260:
1233:
1207:
1198:
Kleinhenz, S.; Pfennig, V.; Seppelt, K. (1998). "Preparation and
Structures of , , , and ".
1177:
1146:
1119:
1114:
Shortland, A. J.; Wilkinson, G. (1973). "Preparation and properties of hexamethyltungsten".
858:
473:
437:
289:
92:
798:. These discoveries helped to spawn re-evaluation of the theoretical considerations for ML
611:
168:
1383:
Kaupp, M. (1998). "The
Nonoctahedral Structures of d0, d1, and d2 Hexamethyl Complexes".
226:
1318:
136:
727:
488:, instead of methyllithium. The stoichiometry of the improved synthesis is as follows:
485:
354:
1614:
2158:
2032:
978:
963:
886:
885:
to form tungsten metal is highly unlikely. The following equation is the approximate
874:
465:
457:
1334:
805:
Other 6-coordinate complexes with distorted trigonal prismatic structures include ,
602:
trigonal prismatic geometry is unusual in that the vast majority of six-coordinate
525:
193:
1458:
1150:
1505:
Matsumoto, S.; Ikeda, O.; Ohmi, K. (Canon K. K., Japan) (1991). "Eur. Pat. Appl".
1326:
746:
trigonal prism in which all six carbon atoms are equivalent is distorted to the C
469:
1397:
10.1002/(SICI)1521-3765(19980904)4:9<1678::AID-CHEM1678>3.0.CO;2-N
1212:
10.1002/(SICI)1521-3765(19980904)4:9<1687::AID-CHEM1687>3.0.CO;2-R
989:
958:. Similarly, acids give methane and unidentified tungsten derivatives, while
314:
147:
468:. The synthesis was motivated in part by previous work which indicated that
425:
1466:
1369:
1158:
1551:
10.1002/(SICI)1099-0739(199803)12:3<155::AID-AOC688>3.0.CO;2-Z
1559:
1237:
1181:
1123:
997:
986:
959:
402:
1423:
1291:
1264:
866:
767:
180:
1437:
Landis, C. K.; Cleveland, T.; Firman, T. K. (1996). "Structure of W(CH
1361:
1068:
Serious explosions have been reported as a result of working with W(CH
17:
1623:
969:
A patent application was submitted in 1991 suggesting the use of W(CH
955:
870:
433:
406:
353:
Except where otherwise noted, data are given for materials in their
782:
be incorrect. Prior to 1989, there was no reason to suspect that ML
992:; however, to date it has not been used for this purpose. Rather,
127:
115:
105:
456:
and
Shortland, who described its preparation by the reaction of
1627:
1577:
Fluorine
Chemistry at the Millennium: Fascinated by Fluorine
210:
47:
37:
758:
Deviation from octahedral geometry can be ascribed to a
476:
compounds are thermally unstable, in the hopes that an
371:
1348:
Seppelt, Konrad (2003). "Nonoctahedral
Structures".
2073:
2048:
1933:
1882:
1802:
1747:
1692:
1661:
690:is indeed trigonal prismatic structure with either
1035:, with U.V. irradiation gives the carbyne complex
736:As shown in the top figure at right, the ideal or
452:Hexamethyltungsten was first reported in 1973 by
192:
91:
1639:
1532:"Chemical vapor deposition of tungsten oxide"
8:
1515:: CS1 maint: multiple names: authors list (
873:. The black residue is purported to contain
722:had a strongly distorted trigonal prismatic
1015:diluted with Ne at −90 °C affords W(CF
877:and tungsten, but the decomposition of W(CH
2045:
1646:
1632:
1624:
225:
155:
52:Ball and stick model of hexamethyltungsten
26:
1558:
1480:Housecroft, C. E.; Sharpe, A. G. (2004).
1109:
1107:
1105:
524:Alternatively, the alkylation can employ
2136:
2132:
2128:
2124:
1223:
1221:
1101:
950:Like many organometallic complexes, WMe
634:was trigonal prismatic as indicated by
271:
246:
221:
1508:
1193:
1191:
733:, which they later confirmed in 1998.
330:Red crystalline solid / Vivid red gas
889:proposed by Wilkinson and Shortland:
253:Key: XWAZCLPCQDERBK-UHFFFAOYSA-N
135:
7:
773:The history of the structure of W(CH
1603:Journal of Organometallic Chemistry
760:second-order Jahn-Teller distortion
682:, Volden et al. confirmed that W(CH
183:
25:
1539:Applied Organometallic Chemistry
638:. They predicted that other d ML
361:
307:
301:
1530:Kirss, R. U.; Meda, L. (1998).
1484:(2nd ed.). Prentice Hall.
966:and leave the tungsten halide.
357:(at 25 °C , 100 kPa).
1139:Journal of Hazardous Materials
1076:, even in the absence of air.
750:structure observed by Seppelt
422:transition metal alkyl complex
295:
1:
1615:10.1016/S0022-328X(00)89324-9
1459:10.1126/science.272.5259.182b
1385:Chemistry: A European Journal
1350:Accounts of Chemical Research
1151:10.1016/j.jhazmat.2005.11.007
853:Reactivity and potential uses
610:. In the initial report, the
608:octahedral molecular geometry
2050:Organotungsten(VI) compounds
1327:10.1126/science.271.5249.626
1230:J. Chem. Soc., Dalton Trans.
1174:J. Chem. Soc., Dalton Trans.
1116:J. Chem. Soc., Dalton Trans.
839:(d), and the aforementioned
786:compounds were anything but
1574:Banks, R. E. (2000-12-04).
710:symmetry. In 1996, Seppelt
575:trigonal prismatic geometry
33:
2191:
983:chemical vapor deposition
351:
334:
282:
262:
237:
75:
67:
62:
32:
2165:Organotungsten compounds
1086:Organometallic chemistry
829:symmetry) include (d),
604:organometallic compounds
250:InChI=1S/6CH3.W/h6*1H3;
977:in the manufacture of
53:
43:
1091:Tungsten hexachloride
1064:Safety considerations
994:tungsten hexafluoride
869:and trace amounts of
861:, hexamethyltungsten
724:coordination geometry
636:X-ray crystallography
462:tungsten hexachloride
430:aromatic hydrocarbons
51:
41:
1238:10.1039/DT9780001403
1182:10.1039/DT9760002235
1124:10.1039/DT9730000872
1031:), which in neat PMe
680:electron diffraction
484:in conjunction with
442:carbon tetrachloride
2074:Polytungstate salts
1482:Inorganic Chemistry
1424:10.1021/ja00111a036
1319:1996Sci...271..626P
1292:10.1021/ja00167a065
1265:10.1021/ja00193a061
764:valence bond theory
678:. Using gas-phase
573:adopts a distorted
347:Trigonal prismatic
322: g·mol
70:Tungsten hexamethyl
29:
28:Hexamethyltungsten
1655:Tungsten compounds
1000:are used instead.
714:reported that W(CH
561:Molecular geometry
482:trimethylaluminium
420:. Classified as a
396:Hexamethyltungsten
384:Infobox references
54:
44:
27:
2152:
2151:
2148:
2147:
1491:978-0-13-039913-7
1453:(5259): 182–183.
1362:10.1021/ar020052o
1286:(11): 4547–4549.
1003:Treatment of W(CH
731:X-ray diffraction
400:chemical compound
392:Chemical compound
390:
389:
206:CompTox Dashboard
117:Interactive image
58:
57:
16:(Redirected from
2182:
2175:Methyl complexes
2170:Gases with color
2140:
2046:
1648:
1641:
1634:
1625:
1619:
1618:
1598:
1592:
1591:
1571:
1565:
1564:
1562:
1536:
1527:
1521:
1520:
1514:
1506:
1502:
1496:
1495:
1477:
1471:
1470:
1434:
1428:
1427:
1418:(6): 1859–1860.
1412:J. Am. Chem. Soc
1407:
1401:
1400:
1380:
1374:
1373:
1345:
1339:
1338:
1302:
1296:
1295:
1280:J. Am. Chem. Soc
1275:
1269:
1268:
1253:J. Am. Chem. Soc
1248:
1242:
1241:
1225:
1216:
1215:
1195:
1186:
1185:
1169:
1163:
1162:
1134:
1128:
1127:
1111:
1059:
1058:
1057:
1049:
1048:
954:is destroyed by
945:
944:
943:
935:
934:
924:
923:
922:
912:
911:
910:
902:
901:
859:room temperature
848:
847:
846:
838:
837:
836:
824:
823:
822:
814:
813:
812:
661:
660:
659:
651:
650:
649:
642:species such as
633:
632:
631:
474:transition metal
438:carbon disulfide
416:also written WMe
374:
368:
365:
364:
321:
309:
303:
297:
290:Chemical formula
230:
229:
214:
212:
196:
185:
169:Gmelin Reference
159:
139:
119:
95:
34:
30:
21:
2190:
2189:
2185:
2184:
2183:
2181:
2180:
2179:
2155:
2154:
2153:
2144:
2138:
2134:
2130:
2126:
2122:
2116:
2112:
2108:
2104:
2100:
2092:
2088:
2084:
2069:
2065:
2061:
2044:
2040:
2036:
2028:
2020:
2012:
2004:
1996:
1988:
1980:
1972:
1964:
1956:
1948:
1944:
1929:
1925:
1917:
1913:
1905:
1897:
1893:
1878:
1874:
1866:
1858:
1850:
1842:
1834:
1826:
1818:
1798:
1794:
1786:
1778:
1770:
1762:
1758:
1743:
1739:
1735:
1727:
1719:
1711:
1703:
1688:
1684:
1680:
1672:
1657:
1652:
1622:
1600:
1599:
1595:
1588:
1573:
1572:
1568:
1534:
1529:
1528:
1524:
1507:
1504:
1503:
1499:
1492:
1479:
1478:
1474:
1444:
1440:
1436:
1435:
1431:
1409:
1408:
1404:
1382:
1381:
1377:
1347:
1346:
1342:
1304:
1303:
1299:
1277:
1276:
1272:
1250:
1249:
1245:
1227:
1226:
1219:
1197:
1196:
1189:
1171:
1170:
1166:
1136:
1135:
1131:
1113:
1112:
1103:
1099:
1082:
1075:
1071:
1066:
1060:in high yield.
1056:
1053:
1052:
1051:
1047:
1044:
1043:
1042:
1040:
1034:
1030:
1026:
1022:
1018:
1014:
1010:
1006:
976:
972:
953:
942:
939:
938:
937:
933:
930:
929:
928:
926:
921:
918:
917:
916:
914:
909:
906:
905:
904:
900:
897:
896:
895:
893:
884:
880:
855:
845:
843:
842:
841:
840:
835:
833:
832:
831:
830:
828:
821:
819:
818:
817:
816:
811:
809:
808:
807:
806:
801:
797:
793:
785:
780:
776:
749:
745:
721:
717:
709:
699:
689:
685:
677:
673:
669:
665:
658:
656:
655:
654:
653:
648:
646:
645:
644:
643:
641:
630:
628:
627:
626:
625:
619:
612:IR spectroscopy
600:
593:
586:
572:
568:
563:
555:
551:
547:
543:
539:
535:
519:
515:
511:
507:
503:
499:
495:
450:
419:
415:
410:
393:
386:
381:
380:
379: ?)
370:
366:
362:
358:
344:
342:Molecular shape
319:
306:
300:
292:
278:
275:
270:
269:
258:
255:
254:
251:
245:
244:
233:
223:DTXSID601027134
215:
208:
199:
186:
171:
162:
142:
122:
109:
98:
85:
71:
23:
22:
15:
12:
11:
5:
2188:
2186:
2178:
2177:
2172:
2167:
2157:
2156:
2150:
2149:
2146:
2145:
2143:
2142:
2119:
2114:
2110:
2106:
2102:
2098:
2094:
2090:
2086:
2082:
2077:
2075:
2071:
2070:
2068:
2067:
2063:
2059:
2054:
2052:
2043:
2042:
2038:
2034:
2030:
2026:
2022:
2018:
2014:
2010:
2006:
2002:
1998:
1994:
1990:
1986:
1982:
1978:
1974:
1970:
1966:
1962:
1958:
1954:
1950:
1946:
1942:
1937:
1935:
1931:
1930:
1928:
1927:
1923:
1919:
1915:
1911:
1907:
1903:
1899:
1895:
1891:
1886:
1884:
1880:
1879:
1877:
1876:
1872:
1868:
1864:
1860:
1856:
1852:
1848:
1844:
1840:
1836:
1832:
1828:
1824:
1820:
1816:
1812:
1806:
1804:
1800:
1799:
1797:
1796:
1792:
1784:
1780:
1776:
1772:
1768:
1764:
1760:
1756:
1751:
1749:
1745:
1744:
1742:
1741:
1737:
1733:
1729:
1725:
1721:
1717:
1713:
1709:
1705:
1701:
1696:
1694:
1690:
1689:
1687:
1686:
1682:
1678:
1674:
1670:
1665:
1663:
1659:
1658:
1653:
1651:
1650:
1643:
1636:
1628:
1621:
1620:
1593:
1586:
1566:
1545:(3): 155–160.
1522:
1497:
1490:
1472:
1442:
1438:
1429:
1402:
1391:(9): 1678–86.
1375:
1356:(2): 147–153.
1340:
1297:
1270:
1243:
1217:
1187:
1164:
1129:
1118:(8): 872–876.
1100:
1098:
1095:
1094:
1093:
1088:
1081:
1078:
1073:
1069:
1065:
1062:
1054:
1045:
1032:
1028:
1024:
1020:
1016:
1012:
1008:
1004:
974:
970:
951:
948:
947:
940:
931:
919:
907:
898:
882:
878:
854:
851:
844:
834:
826:
820:
810:
799:
795:
791:
783:
778:
774:
770:calculations.
747:
740:
728:single-crystal
719:
715:
704:
694:
687:
683:
675:
671:
667:
663:
657:
647:
639:
629:
617:
598:
594:framework and
591:
581:
570:
566:
562:
559:
558:
557:
553:
549:
545:
541:
537:
533:
522:
521:
517:
513:
509:
505:
501:
497:
493:
486:trimethylamine
449:
446:
417:
413:
408:
391:
388:
387:
382:
360:
359:
355:standard state
352:
349:
348:
345:
340:
337:
336:
332:
331:
328:
324:
323:
317:
311:
310:
304:
298:
293:
288:
285:
284:
280:
279:
277:
276:
274:C(C)(C)(C)(C)C
273:
265:
264:
263:
260:
259:
257:
256:
252:
249:
248:
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239:
238:
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204:
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150:
144:
143:
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132:
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124:
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100:
99:
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96:
88:
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81:
78:
77:
73:
72:
69:
65:
64:
60:
59:
56:
55:
45:
24:
14:
13:
10:
9:
6:
4:
3:
2:
2187:
2176:
2173:
2171:
2168:
2166:
2163:
2162:
2160:
2141:
2120:
2118:
2095:
2093:
2079:
2078:
2076:
2072:
2066:
2056:
2055:
2053:
2051:
2047:
2041:
2031:
2029:
2023:
2021:
2015:
2013:
2007:
2005:
1999:
1997:
1991:
1989:
1983:
1981:
1975:
1973:
1967:
1965:
1959:
1957:
1951:
1949:
1939:
1938:
1936:
1932:
1926:
1920:
1918:
1908:
1906:
1900:
1898:
1888:
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1748:Tungsten(III)
1746:
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1587:9780080531793
1583:
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1567:
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1560:2027.42/38321
1556:
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1359:
1355:
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1344:
1341:
1336:
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1328:
1324:
1320:
1316:
1313:(5249): 626.
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1298:
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1125:
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1038:
1001:
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988:
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980:
979:semiconductor
967:
965:
964:methyl halide
961:
957:
892:
891:
890:
888:
887:stoichiometry
876:
875:polymethylene
872:
868:
864:
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803:
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531:
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489:
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475:
471:
467:
466:diethyl ether
463:
459:
458:methyllithium
455:
447:
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50:
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36:
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31:
19:
2057:
1934:Tungsten(VI)
1803:Tungsten(IV)
1788:
1693:Tungsten(II)
1606:
1602:
1596:
1580:. Elsevier.
1576:
1569:
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1310:
1306:
1300:
1283:
1279:
1273:
1259:(11): 4114.
1256:
1252:
1246:
1232:(10): 1403.
1229:
1203:
1200:Chem. Eur. J
1199:
1176:(21): 2235.
1173:
1167:
1142:
1138:
1132:
1115:
1067:
1039:-WMe(:::CMe)
1036:
1002:
981:devices for
968:
949:
865:, releasing
856:
804:
802:geometries.
772:
757:
751:
742:
737:
735:
711:
706:
701:
696:
691:
623:
615:
595:
583:
578:
564:
526:dimethylzinc
523:
451:
395:
394:
76:Identifiers
68:Other names
1883:Tungsten(V)
1662:Tungsten(0)
1206:(9): 1687.
1145:(1): 1–19.
621:structure.
556:(X = F, Cl)
470:tetrahedral
327:Appearance
283:Properties
137:CHEBI:30522
2159:Categories
1609:(3): C65.
1097:References
990:thin films
863:decomposes
788:octahedral
662:, and W(CH
590:for the WC
512:+ 6 Al(CH
478:octahedral
335:Structure
315:Molar mass
148:ChemSpider
104:3D model (
93:36133-73-0
83:CAS Number
1511:cite news
962:give the
726:based on
536:+ 3 Zn(CH
496:+ 6 Al(CH
454:Wilkinson
448:Synthesis
426:petroleum
1467:17791392
1370:12589700
1335:97242475
1159:16343746
1080:See also
998:hydrogen
987:tungsten
960:halogens
588:symmetry
552:+ 3 ZnX
157:11659456
1447:Science
1315:Bibcode
1307:Science
867:methane
768:VALBOND
544:→ W(CH
504:→ W(CH
472:methyl
398:is the
377:what is
375: (
181:PubChem
174:505585
2127:[H
1584:
1488:
1465:
1368:
1333:
1157:
1011:with F
956:oxygen
871:ethane
815:, and
752:et al.
712:et al.
606:adopt
440:, and
434:ethers
372:verify
369:
320:274.05
267:SMILES
194:142049
63:Names
18:C6H18W
1736:(hpp)
1724:W(OH)
1677:W(PMe
1669:W(CO)
1535:(PDF)
1331:S2CID
1037:trans
849:(d).
577:with
460:with
242:InChI
128:ChEBI
106:JSmol
2058:W(CH
2017:WOCl
2009:WOBr
1922:LiWF
1582:ISBN
1517:link
1486:ISBN
1463:PMID
1366:PMID
1155:PMID
1041:(PMe
1027:(PMe
996:and
913:→ 3
894:W(CH
766:and
565:W(CH
2097:(NH
2025:WOF
2001:WAs
1961:WCl
1953:WBr
1902:WBr
1863:WBr
1855:WCl
1839:WTe
1831:WSe
1791:Bu)
1767:WCl
1708:WCl
1700:WSi
1611:doi
1555:hdl
1547:doi
1455:doi
1451:272
1445:".
1420:doi
1416:117
1393:doi
1358:doi
1323:doi
1311:271
1288:doi
1284:112
1261:doi
1257:111
1234:doi
1208:doi
1178:doi
1147:doi
1143:136
1120:doi
985:of
946:+ W
927:(CH
857:At
700:or
492:WCl
464:in
211:EPA
184:CID
2161::
2137:40
2133:12
2123:Na
2115:42
2111:12
2105:(H
2103:10
2091:40
2087:12
2085:PW
2037:WO
1993:WS
1985:WO
1977:WN
1969:WF
1945:Cl
1941:WO
1916:10
1914:Cl
1871:WI
1847:WF
1823:WS
1815:WO
1810:WC
1787:(O
1775:WI
1716:WI
1607:97
1605:.
1553:.
1543:12
1541:.
1537:.
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1509:{{
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1354:36
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1309:.
1282:.
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1220:^
1202:.
1190:^
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1141:.
1104:^
925:+
915:CH
827:3h
748:3v
652:,
532:WX
528::
520:Cl
444:.
436:,
432:,
428:,
407:CH
305:18
2139:]
2135:O
2131:W
2129:2
2125:6
2117:)
2113:O
2109:W
2107:2
2101:)
2099:4
2089:O
2083:3
2081:H
2064:6
2062:)
2060:3
2039:4
2035:2
2033:H
2027:4
2019:4
2011:4
2003:2
1995:3
1987:3
1979:2
1971:6
1963:6
1955:6
1947:2
1943:2
1924:6
1912:2
1910:W
1904:5
1896:5
1894:O
1892:2
1890:W
1873:4
1865:4
1857:4
1849:4
1841:2
1833:2
1825:2
1817:2
1793:6
1789:t
1785:2
1783:W
1777:3
1769:3
1761:3
1759:O
1757:2
1755:W
1738:4
1734:2
1732:W
1726:2
1718:2
1710:2
1702:2
1683:6
1681:)
1679:3
1671:6
1647:e
1640:t
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1613::
1590:.
1563:.
1557::
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1469:.
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1439:3
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1422::
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1395::
1389:4
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1360::
1337:.
1325::
1317::
1294:.
1290::
1267:.
1263::
1240:.
1236::
1214:.
1210::
1204:4
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1180::
1161:.
1149::
1126:.
1122::
1074:6
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1070:3
1055:4
1050:)
1046:3
1033:3
1029:3
1025:6
1021:6
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1017:3
1013:2
1009:6
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1005:3
975:6
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971:3
952:6
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936:)
932:3
920:4
908:6
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899:3
883:6
881:)
879:3
800:6
796:6
794:)
792:3
784:6
779:6
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775:3
743:h
741:3
738:D
720:6
718:)
716:3
707:v
705:3
702:C
697:h
695:3
692:D
688:6
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684:3
676:6
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672:3
668:6
666:)
664:3
640:6
618:h
616:O
599:3
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592:6
584:v
582:3
579:C
571:6
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567:3
554:2
550:6
548:)
546:3
542:2
540:)
538:3
534:6
518:2
516:)
514:3
510:6
508:)
506:3
502:3
500:)
498:3
494:6
418:6
414:6
412:)
409:3
405:(
403:W
367:N
308:W
302:H
299:6
296:C
213:)
209:(
108:)
20:)
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