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Carbanion

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2311: 1284: 215: 2296: 592: 1577: 735:, respectively, by metathesis of the corresponding organosodium reagent with tetramethylammonium chloride. Since tetramethylammonium cations cannot form a chemical bond to the carbanionic center, these species are believed to contain free carbanions. While the structure of the former was verified by X-ray crystallography almost a century later, the instability of the latter has so far precluded structural verification. The reaction of the putative " 1199: 2257: 223: 1806: 1938: 2219: 1049: 1547: 1779: 1433: 1166: 1107: 1024: 243:
effective charge delocalization. As a consequence, alkyl carbanions with neighboring conjugating groups (e.g., allylic anions, enolates, nitronates, etc.) are generally planar rather than pyramidized. Likewise, delocalized alkenyl carbanions sometimes favor a linear instead of bent geometry. More often, a bent geometry is still preferred for substituted alkenyl anions, though the linear geometry is only
1229: 1462: 1726: 1347: 1905: 1258: 1664: 1988: 1693: 1839: 1759: 1492: 1372: 1402: 1318: 1872: 1606: 1522: 1140: 1078: 1635: 897:(DMSO), which has a broader useful range (~0 to ~35) than values determined in water (~0 to ~14) and better reflect the basicity of the carbanions in typical organic solvents. Values below less than 0 or greater than 35 are indirectly estimated; hence, the numerical accuracy of these values is limited. Aqueous p 2070:
decreases) when the negative charge is delocalized. This effect occurs when the substituents on the carbanion are unsaturated and/or electronegative. Although carbon acids are generally thought of as acids that are much weaker than "classical" Brønsted acids like acetic acid or phenol, the cumulative
904:
values are also commonly encountered in the literature, particularly in the context of biochemistry and enzymology. Moreover, aqueous values are often given in introductory organic chemistry textbooks for pedagogical reasons, although the issue of solvent dependence is often glossed over. In general,
325:
Carbanions, especially ones derived from weak carbon acids that do not benefit sufficiently from the two stabilizing factors listed above, are generally oxygen- and water-sensitive to varying degrees. While some merely degrade and decompose over several weeks or months upon exposure to air, others
371:
In fact, true carbanions (i.e., a species not attached to a stabilizing covalently bound metal) without electron-withdrawing and/or conjugating substituents are not available in the condensed phase, and these species must be studied in the gas phase. For some time, it was not known whether simple
242:
carbanions may deviate from these geometries. Instead of residing in a hybrid orbital, the carbanionic lone pair may instead occupy a p orbital (or an orbital of high p character). A p orbital has a more suitable shape and orientation to overlap with the neighboring π system, resulting in more
367:
sense. However, they are really clusters or complexes containing a polar covalent bond, though with electron density heavily polarized toward the carbon atom. The more electropositive the attached metal atom, the closer the behavior of the reagent is to that of a true carbanion.
399:
was predicted to be negative). Such a species would decompose immediately by spontaneous ejection of an electron and would therefore be too fleeting to observe directly by mass spectrometry. However, in 1978, the methanide anion was unambiguously synthesized by subjecting
3205:
Kütt, Agnes; Rodima, Toomas; Saame, Jaan; Raamat, Elin; Mäemets, Vahur; Kaljurand, Ivari; Koppel, Ilmar A.; Garlyauskayte, Romute Yu.; Yagupolskii, Yurii L.; Yagupolskii, Lev M.; Bernhardt, Eduard; Willner, Helge; Leito, Ivo (2011). "Equilibrium Acidities of Superacids".
177:
are commonly treated and referred to as "carbanions." This is a convenient approximation, although these species are generally clusters or complexes containing highly polar, but still covalent bonds metal–carbon bonds (M–C) rather than true carbanions.
210:
makes similar predictions. This contrasts with carbocations, which have a preference for unoccupied nonbonding orbitals of pure atomic p character, leading to planar and linear geometries, respectively, for alkyl and alkenyl
646:
are 145 pm with the phenyl ring propellered at an average angle of 31.2°. This propeller shape is less pronounced with a tetramethylammonium counterion. A crystal structure for the analogous diphenylmethanide anion
2419:) and in 1914 he demonstrated how triarylmethyl radicals could be reduced to carbanions by alkali metals The phrase carbanion was introduced by Wallis and Adams in 1933 as the negatively charged counterpart of the 279:), whose negative charge is stabilized by delocalization, has an inversion barrier of only 4 kcal/mol (17 kJ/mol), reflecting stabilization of the linear transition state by better π delocalization. 206:, placement of the carbanionic lone pair electrons in an orbital with significant s character is favorable, accounting for the pyramidalized and bent geometries of alkyl and alkenyl carbanions, respectively. 2310: 525:
are −6, −7.4, −3.6 kcal/mol, respectively) indicating that α substitution is destabilizing. However, relatively modest stabilizing effects can render them bound. For example,
912:
values in water and organic solvent diverge significantly when the anion is capable of hydrogen bonding. For instance, in the case of water, the values differ dramatically: the p
2460: 861:
values allow the prediction of whether a proton transfer process will be thermodynamically favorable: In order for the deprotonation of an acidic species HA with base
557:
stabilization. Gas-phase carbanions that are sp and sp hybridized are much more strongly stabilized and are often prepared directly by gas-phase deprotonation.
2647:
Ellison, G. Barney; Engelking, P. C.; Lineberger, W. C. (April 1978). "An experimental determination of the geometry and electron affinity of methyl radical".
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2-methyloctanoic acid, which could only have formed from likewise optically active 2-methylheptyllithium with the carbon atom linked to lithium the carbanion:
700:≈ 43) was unsuccessful, due to rapid reaction of the formed anion with the THF solvent. The free benzyl anion has also been generated in the solution phase by 3154:
Trummal, Aleksander; Lipping, Lauri; Kaljurand, Ivari; Koppel, Ilmar A.; Leito, Ivo (2016-05-06). "Acidity of Strong Acids in Water and Dimethyl Sulfoxide".
2071:(additive) effect of several electron accepting substituents can lead to acids that are as strong or stronger than the inorganic mineral acids. For example, 815: 560:
In the condensed phase only carbanions that are sufficiently stabilized by delocalization have been isolated as truly ionic species. In 1984, Olmstead and
158: 2295: 130:
Carbanions have a concentration of electron density at the negatively charged carbon, which, in most cases, reacts efficiently with a variety of
2548: 747:" with water was reported to liberate toluene and tetramethylammonium hydroxide and provides indirect evidence for the claimed formulation. 2005:
Note that acetic acid, ammonia, aniline, ethanol, and hydrogen chloride are not carbon acids, but are common acids shown for comparison.
2190:
The first ever evidence for the existence of chiral organolithium compounds was obtained in 1950. Reaction of chiral 2-iodooctane with
411:
was determined by photoelectron spectroscopy to be +1.8 kcal/mol, making it a bound species, but just barely so. The structure of
3372:
Kapeller, Dagmar (2007). "Preparation of Chiral α-Oxy-methyllithiums of 99% ee and Determination of Their Configurational Stability".
3089:
Bordwell, G. F.; Matthews, Walter S. (2002-05-01). "Equilibrium acidities of carbon acids. III. Carbon acids in the membrane series".
591: 3031: 847:). As conjugate acid–base pairs, the factors that determine the relative stability of carbanions also determine the ordering of the p 2715:
Olmstead, Marilyn M. (1985). "The isolation and X-ray structures of lithium crown ether salts of the free phenyl carbanions and ".
2691: 2140:
values in the range of 55 to 65. The range of acid dissociation constants for carbon acids thus spans over 70 orders of magnitude.
2890: 2755: 3581: 3561: 2175:, because if the activation barrier for inversion of this geometry is too low any attempt at introducing chirality will end in 790:
if deprotonation results in loss of a proton from a carbon atom. Compared to compounds typically considered to be acids (e.g.,
3318:-2-Methylcyclopropyllithium and Some Observations on the Stereochemistry of their Reactions with Bromine and Carbon Dioxide". 3119:
Russell, Jamie; Roques, Nicolas (1998-11-05). "Effective nucleophilic trifluoromethylation with fluoroform and common base".
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On heating the reaction to 0 °C the optical activity is lost. More evidence followed in the 1960s. A reaction of the
2344: 2912:
Kasmai, Hamid S. (June 1999). "A Simple and Convenient Method for Generation and NMR Observation of Stable Carbanions".
2406: 2168: 2218: 2183:. However, solid evidence exists that carbanions can indeed be chiral for example in research carried out with certain 334:) are unusual in being indefinitely stable under dry air and hydrolyzing only very slowly in the presence of moisture. 786:
Any compound containing hydrogen can, in principle, undergo deprotonation to form its conjugate base. A compound is a
291:
and basic. The basicity and nucleophilicity of carbanions are determined by the substituents on carbon. These include
2777:
Bockrath, Bradley; Dorfman, Leon M. (2002-05-01). "Submicrosecond formation and observation of reactive carbanions".
2147:
compounds enables these compounds to participate in synthetically important C–C bond-forming reactions including the
202:
alkyl, alkenyl/aryl, and alkynyl carbanions assume trigonal pyramidal, bent, and linear geometries, respectively. By
322:
of the charge-bearing carbanion. The greater the s-character of the charge-bearing atom, the more stable the anion.
2941:"pKa values in the undergraduate curriculum: introducing pKa values measured in DMSO to illustrate solvent effects" 2325: 2287: 819: 806:), carbon acids are typically many orders of magnitude weaker, although exceptions exist (see below). For example, 3469:
Wallis, E. S.; Adams, F. H. (1933). "The Spatial Configuration of the Valences in Tricovalent Carbon Compounds1".
3345:
Walborsky, H. M. (1964). "Cyclopropanes. XV. The Optical Stability of 1-Methyl-2,2-diphenylcyclopropyllithium".
2492:"The influence of electron-withdrawing substituents on the geometries and barriers to inversion of vinyl anions" 2229: 2361:. Once again in the range of −78 °C to 0 °C the chirality is preserved in this reaction sequence. ( 1915: 364: 349: 2133:
well below −10. On the other end of the scale, hydrocarbons bearing only alkyl groups are thought to have p
2410: 541:
anions are also bound, as a result of negative hyperconjugation of the lone pair with the β-substituent (n
2172: 319: 307: 191: 170: 162: 108: 96: 88: 1283: 330:). Among commonly encountered carbanionic reagents in the laboratory, ionic salts of hydrogen cyanide ( 214: 3163: 3001: 2593: 2382: 840: 2355: 829: 428: 267:, has an inversion barrier of 27 kcal/mol (110 kJ/mol), while allenyl anion or allenide, 3519: 3187: 2611: 2362: 2180: 2164: 1209: 965: 147: 538: 3389: 3265: 3223: 3179: 3136: 2960: 2894: 2859: 2759: 2697: 2687: 2682:
Blanksby, S. J.; Bowie, J. H. (2005). "Carbanions: formation, structure and thermochemistry".
2664: 2629: 2544: 2511: 1948: 1882: 926:
in DMSO of water is 31.4, reflecting the differing ability of water and DMSO to stabilize the
894: 673:= 32.3), was also obtained. However, the attempted isolation of a complex of the benzyl anion 389: 303: 187: 174: 166: 31: 326:
may react vigorously and exothermically with air almost immediately to spontaneously ignite (
310:
can stabilize the anion. This is especially true when the anion is stabilized as a result of
3509: 3478: 3451: 3420: 3381: 3354: 3327: 3292: 3257: 3215: 3171: 3128: 3098: 3071: 3009: 2952: 2921: 2886: 2851: 2820: 2786: 2751: 2724: 2656: 2619: 2601: 2536: 2503: 2474: 2370: 2366: 2210: 2152: 1769: 1703: 1328: 763: 759: 609: 572: 568: 296: 256: 76: 1576: 372:
alkyl anions could exist as free species; many theoretical studies predicted that even the
222: 3576: 3045: 2390: 2386: 2198: 2086: 2072: 1645: 1443: 1239: 931: 799: 755: 708: 3167: 3005: 2597: 1805: 3241:
Ding, Feizhi; Smith, Jeremy M.; Wang, Haobin (2009). "First-Principles Calculation of p
3062:
Bordwell, Frederick G. (1988). "Equilibrium acidities in dimethyl sulfoxide solution".
2148: 2119: 1965: 1937: 1198: 833: 811: 602: 576: 203: 135: 50: 3132: 2811:[On triphenylmethyl and analogues of triphenylmethyl in the biphenyl series]. 2624: 2565: 2491: 1048: 3570: 2507: 2441: 2420: 2240: 2184: 2108: 1816: 1736: 775: 327: 80: 3523: 3283:
Letsinger, Robert L. (1950). "Formation of Optically Active 1-Methylheptyllithium".
3191: 2470: 1546: 2381:
A carbanionic structure first made an appearance in the reaction mechanism for the
2206: 2191: 2176: 2028: 1778: 1674: 1472: 1432: 1268: 791: 561: 338: 288: 207: 131: 1228: 1165: 1106: 1023: 259:. For instance, calculations indicate that the parent vinyl anion or ethylenide, 3013: 2465: 2431: 2348: 1789: 1557: 1005: 803: 795: 643: 631: 583: 565: 526: 311: 116: 2956: 2586:
Proceedings of the National Academy of Sciences of the United States of America
1904: 1725: 1346: 3440:"Über Metalladditionen an freie organische Radikale. XII. Über Triarylmethyle" 1663: 1532: 1461: 1357: 1257: 828:
of 49 which may undergo deprotonation in the presence of a superbase like the
814:
sense, since its aqueous solutions are neutral. Nevertheless, it is very weak
751: 701: 533:
anions are bound due to increased s character of the lone pair orbital, while
3455: 3175: 3140: 2964: 2940: 2863: 2855: 2824: 2809:"Ueber Triphenylmethyl und Analoga des Triphenylmethyls in der Biphenylreihe" 2668: 2530: 2515: 2469:, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) " 3514: 3497: 2701: 2478: 2332: 1987: 927: 534: 373: 195: 124: 3442:[On metal addition to free organic radicals. XII. Tryarylmethyls]. 3393: 3269: 3227: 3183: 2898: 2763: 2633: 2118:
values that indicate complete or nearly complete proton transfer to water.
1838: 1758: 2686:. Gross, Michael L., Caprioli, R. M. (1st ed.). Amsterdam: Elsevier. 2606: 2540: 2251:
isomer would have indicated that the intermediate carbanion was unstable.
1692: 1491: 17: 3424: 2891:
10.1002/1521-3765(20020715)8:14<3229::AID-CHEM3229>3.0.CO;2-3
2756:
10.1002/1521-3765(20020715)8:14<3229::AID-CHEM3229>3.0.CO;2-3
2283: 2144: 1849: 1587: 1382: 1176: 586:(which forms a stable complex with lithium cations) at low temperatures: 299:. Electronegative atoms adjacent to the charge will stabilize the charge; 3482: 3358: 3331: 3296: 3102: 3075: 2790: 2728: 2660: 2336: 2202: 2123: 1502: 1412: 1371: 1294: 1150: 1117: 1088: 1059: 1034: 807: 331: 143: 104: 92: 84: 3385: 3261: 3219: 2925: 2615: 1616: 550: 530: 445:
Simple primary, secondary and tertiary sp carbanions (e.g., ethanide
401: 154: 100: 43: 3439: 3408: 2839: 2808: 1871: 1605: 2532:
Stereoelectronic Effects: A Bridge Between Structure and Reactivity
1401: 1317: 2877:
Harder, Sjoerd (2002-07-15). "Schlenk's Early "Free" Carbanions".
1634: 1521: 1139: 1077: 554: 139: 112: 39: 3310:
Applequist, Douglas E. (1961). "The Configurational Stability of
774:
NMR has provided structural and reactivity data for a variety of
234:
isomers that undergo inversion through a linear transition state.
2436: 120: 489:
were subsequently determined to be unbound species (the EAs of
955: 627: 3498:"The first century of physical organic chemistry: A prologue" 2309: 2299:
Optical stability of 1-methyl-2,2-diphenylcyclopropyllithium
2294: 2255: 2217: 590: 404:
to an electric discharge, and the electron affinity (EA) of
247:
less stable, resulting in facile equilibration between the (
758:
in DMSO shows four vinylic protons at 6.5 ppm and two
226:
Vinyl anions are bent. 1,2-Disubstituted vinyl anions have
2985:
Values in the Undergraduate Curriculum: What is the Real p
2566:"Electron Affinity of the Methyl Radical: Structures of CH 2247:-2-methylcyclopropylcarboxylic acid. The formation of the 766:
anion has a single resonance at 5.50 ppm. The use of
2978:
Silverstein, Todd P.; Heller, Stephen T. (2017-04-17). "p
952: 2742:
Harder, S. (2002). "Schlenk's Early "Free" Carbanions".
2063:
As indicated by the examples above, acidity increases (p
854:
values of the corresponding carbon acids. Furthermore, p
750:
One tool for the detection of carbanions in solution is
190:, the negative charge of a carbanion is localized in an 2939:
Heller, Stephen T.; Silverstein, Todd P. (2020-04-23).
363:) are often referred to as "carbanions," at least in a 2171:
the question is whether or not carbanions can display
971:
These values may differ significantly from aqueous p
208:
Valence shell electron pair repulsion (VSEPR) theory
2305:Of recent date are chiral methyllithium compounds: 3248:Values for Organic Acids in Nonaqueous Solution". 2807:Schlenk, W.; Weickel, T.; Herzenstein, A. (1910). 2490:Caramella, Pierluigi; Houk, K. N. (1981-01-01). 2314:Chiral oxymethyllithiums. Bu stands for butyl, 634:results in a red solution and the salt complex 255:) isomers of the (bent) anion through a linear 3444:Berichte der Deutschen Chemischen Gesellschaft 2844:Berichte der Deutschen Chemischen Gesellschaft 2535:. Chichester, UK: John Wiley & Sons, Ltd. 2331:contains a chiral group with a hydrogen and a 711:prepared two red-colored salts, formulated as 3413:Journal of the Chemical Society, Transactions 2564:Marynick, Dennis S.; Dixon, David A. (1977). 2339:group is replaced by lithium to intermediate 642:precipitates at −20 °C. The central C–C 8: 3409:"LXV. An extension of the benzoin synthesis" 934:, the numerical values are comparable: the p 2122:, with three strongly electron-withdrawing 2842:[On benzyl tetramethyl ammonium]. 1986: 1936: 1757: 1724: 1691: 1545: 1370: 1282: 1197: 1164: 1022: 3513: 2623: 2605: 2405:in a quest for tetramethylammonium (from 2354:which on reaction with acetic acid gives 2282:-butyllithium followed by quenching with 2201:at −70 °C followed by reaction with 2111:HCNO, are all strong acids with aqueous p 2038:in DMSO was estimated by the correlation 571:of the triphenylmethanide carbanion from 218:An alkyl carbanion is trigonal pyramidal. 27:Ion with a negatively charged carbon atom 3471:Journal of the American Chemical Society 3374:Journal of the American Chemical Society 3347:Journal of the American Chemical Society 3320:Journal of the American Chemical Society 3285:Journal of the American Chemical Society 3091:Journal of the American Chemical Society 2779:Journal of the American Chemical Society 2717:Journal of the American Chemical Society 2649:Journal of the American Chemical Society 2413: 2400: 2396: 2266:In the same manner the reaction of (+)-( 2102: 2098: 2091: 2081: 2077: 1980: 1976: 1972: 1930: 1926: 1922: 1897: 1893: 1889: 1864: 1860: 1856: 1831: 1827: 1823: 1797: 1751: 1747: 1743: 1718: 1714: 1710: 1685: 1681: 1656: 1652: 1627: 1623: 1598: 1594: 1568: 1564: 1539: 1513: 1509: 1483: 1479: 1454: 1450: 1424: 1420: 1393: 1389: 1364: 1339: 1335: 1310: 1306: 1302: 1275: 1250: 1246: 1220: 1216: 1191: 1187: 1183: 1158: 1132: 1128: 1124: 1099: 1095: 1070: 1066: 1041: 1016: 1012: 742: 738: 730: 726: 718: 714: 695: 669: 665: 650: 637: 622: 520: 516: 508: 504: 496: 492: 484: 480: 468: 464: 448: 434: 407: 395: 388:should be an unbound species (i.e., the 359: 355: 344: 274: 270: 262: 221: 213: 67: 63: 3407:Clarke, R. W. L.; Lapworth, A. (1907). 2453: 2013: 595:Formation of the triphenylmethane anion 549:). The same holds true for anions with 2278:-methyl-2,2-diphenylcyclopropane with 919:in water of water is 14.0, while the p 3114: 3112: 3025: 3023: 2802: 2800: 2684:The encyclopedia of mass spectrometry 7: 2838:Schlenk, W.; Holtz, Johanna (1917). 2385:as correctly proposed by Clarke and 2235:of 2-methylcyclopropyl bromide with 431:barrier of 1.3 kcal/mol, while 3156:The Journal of Physical Chemistry A 3030:Evans, D. A.; Ripin, D. H. (2005). 2345:phosphate–phosphorane rearrangement 865:to be thermodynamically favorable ( 655:), prepared form diphenylmethane (p 2840:"Über Benzyl-tetramethyl-ammonium" 2813:Justus Liebig's Annalen der Chemie 2466:Compendium of Chemical Terminology 427:) with an H−C−H angle of 108° and 194:hybridized orbital on carbon as a 25: 2260:Stereochemistry of organolithiums 2143:The acidity of the α-hydrogen in 3438:Schlenk, W.; Marcus, E. (1914). 3250:The Journal of Organic Chemistry 3208:The Journal of Organic Chemistry 2529:Alabugin, Igor V. (2016-09-19). 2239:-butyllithium again followed by 1903: 1870: 1837: 1804: 1777: 1662: 1633: 1604: 1575: 1520: 1490: 1460: 1431: 1400: 1345: 1316: 1256: 1227: 1138: 1105: 1076: 1047: 810:is not an acid in the classical 630:at low temperatures followed by 161:. A carbanion is one of several 134:of varying strengths, including 2167:for a carbanion described as a 146:, halogenating reagents (e.g., 2879:Chemistry – A European Journal 2222:Optically active organolithium 930:anion. On the other hand, for 438:was determined to be planar (D 1: 3560:values at daecr1.harvard.edu 3133:10.1016/S0040-4020(98)00846-1 3064:Accounts of Chemical Research 2994:Journal of Chemical Education 2914:Journal of Chemical Education 2744:Chemistry: A European Journal 762:protons at 3 ppm whereas the 337:Organometallic reagents like 79:. The carbanions formed from 49:Formally, a carbanion is the 3553:Large database of Bordwell p 3547:values at www.chem.wisc.edu 3540:Large database of Bordwell p 2508:10.1016/0040-4039(81)80005-6 2407:tetramethylammonium chloride 2095:, pentacyanocyclopentadiene 423:was found to be pyramidal (C 3014:10.1021/acs.jchemed.6b00623 941:in water is 15, while the p 869:> 1), the relationship p 3598: 3502:Pure and Applied Chemistry 2957:10.1007/s40828-020-00112-z 2369:after derivatization with 2288:retention of configuration 2126:groups, has an estimated p 318:Geometry also affects the 2318:-Pr stands for isopropyl. 2286:resulted in product with 954:Carbon acid acidities by 287:Carbanions are typically 3456:10.1002/cber.19140470256 3176:10.1021/acs.jpca.6b02253 2856:10.1002/cber.19170500143 2825:10.1002/jlac.19103720102 886:These values below are p 707:Early in 1904 and 1917, 169:. In organic synthesis, 127:) anions, respectively. 3515:10.1351/pac199769020211 3496:Tidwell, T. T. (1997). 2479:10.1351/goldbook.C00804 2205:yielded mostly racemic 1916:Hexafluoroacetylacetone 830:Lochmann–Schlosser base 350:methylmagnesium bromide 103:(at an sp carbon), and 75:where B stands for the 46:is negatively charged. 3582:Reactive intermediates 2319: 2300: 2261: 2223: 2209:but also an amount of 596: 564:presented the lithium 235: 219: 171:organolithium reagents 163:reactive intermediates 2607:10.1073/pnas.74.2.410 2541:10.1002/9781118906378 2313: 2298: 2259: 2243:with dry ice yielded 2221: 2031:(MeCN) is −3.7. The p 893:values determined in 594: 320:orbital hybridization 283:Trends and occurrence 225: 217: 111:carbon) are known as 3425:10.1039/CT9079100694 2383:benzoin condensation 2207:2-methylbutyric acid 704:of dibenzylmercury. 341:(hexameric cluster, 198:. As a consequence, 3483:10.1021/ja01336a068 3359:10.1021/ja01070a017 3332:10.1021/ja01465a030 3297:10.1021/ja01166a538 3168:2016JPCA..120.3663T 3127:(45): 13771–13782. 3103:10.1021/ja00811a041 3076:10.1021/ar00156a004 3006:2017JChEd..94..690S 2791:10.1021/ja00825a005 2729:10.1021/ja00293a059 2661:10.1021/ja00476a054 2598:1977PNAS...74..410M 2496:Tetrahedron Letters 990:Structural formula 980: 2365:was determined by 2363:Enantioselectivity 2343:which undergoes a 2320: 2301: 2262: 2224: 2181:nitrogen inversion 2165:molecular geometry 1210:Dimethyl sulfoxide 953: 818:with an estimated 597: 236: 220: 3386:10.1021/ja066183s 3353:(16): 3283–3288. 3262:10.1021/jo802641r 3220:10.1021/jo101409p 3162:(20): 3663–3669. 2926:10.1021/ed076p830 2885:(14): 3229–3232. 2785:(18): 5708–5715. 2750:(14): 3229–3232. 2550:978-1-118-90637-8 2389:in 1907. In 1904 2335:substituent. The 2179:, similar to the 2159:Chiral carbanions 2006: 1997: 1996: 1949:Hydrogen chloride 979: 895:dimethylsulfoxide 390:electron affinity 308:Resonance effects 175:Grignard reagents 167:organic chemistry 151:-bromosuccinimide 32:organic chemistry 16:(Redirected from 3589: 3528: 3527: 3517: 3493: 3487: 3486: 3466: 3460: 3459: 3435: 3429: 3428: 3404: 3398: 3397: 3369: 3363: 3362: 3342: 3336: 3335: 3307: 3301: 3300: 3280: 3274: 3273: 3256:(7): 2679–2691. 3238: 3232: 3231: 3202: 3196: 3195: 3151: 3145: 3144: 3116: 3107: 3106: 3097:(4): 1216–1217. 3086: 3080: 3079: 3059: 3053: 3052: 3050: 3044:. Archived from 3043: 3027: 3018: 3017: 2975: 2969: 2968: 2936: 2930: 2929: 2909: 2903: 2902: 2874: 2868: 2867: 2835: 2829: 2828: 2804: 2795: 2794: 2774: 2768: 2767: 2739: 2733: 2732: 2723:(7): 2174–2175. 2712: 2706: 2705: 2679: 2673: 2672: 2655:(8): 2556–2558. 2644: 2638: 2637: 2627: 2609: 2581: 2580: 2579: 2561: 2555: 2554: 2526: 2520: 2519: 2487: 2481: 2458: 2417: 2404: 2367:NMR spectroscopy 2211:optically active 2169:trigonal pyramid 2153:Michael addition 2106: 2094: 2084: 2057: 2055: 2018: 2004: 1990: 1983: 1940: 1933: 1907: 1900: 1874: 1867: 1841: 1834: 1808: 1801: 1781: 1770:Hydrogen cyanide 1761: 1754: 1728: 1721: 1704:Diethyl malonate 1695: 1688: 1666: 1659: 1637: 1630: 1608: 1601: 1579: 1572: 1549: 1542: 1524: 1517: 1494: 1487: 1464: 1457: 1435: 1428: 1404: 1397: 1374: 1367: 1349: 1342: 1329:Triphenylmethane 1320: 1313: 1286: 1279: 1260: 1253: 1231: 1224: 1201: 1194: 1168: 1161: 1142: 1135: 1109: 1102: 1080: 1073: 1051: 1044: 1026: 1019: 981: 970: 883:(AH) must hold. 864: 800:carboxylic acids 773: 769: 764:cyclopentadienyl 760:methylene bridge 754:. A spectrum of 746: 734: 722: 702:pulse radiolysis 699: 684: 683: 682: 679: 672: 654: 641: 625: 610:triphenylmethane 573:triphenylmethane 524: 512: 500: 488: 472: 460: 459: 458: 455: 437: 422: 421: 420: 417: 410: 398: 387: 386: 385: 382: 362: 352:(ether complex, 347: 297:inductive effect 278: 266: 257:transition state 188:π delocalization 71: 21: 3597: 3596: 3592: 3591: 3590: 3588: 3587: 3586: 3567: 3566: 3559: 3546: 3537: 3532: 3531: 3495: 3494: 3490: 3468: 3467: 3463: 3437: 3436: 3432: 3406: 3405: 3401: 3371: 3370: 3366: 3344: 3343: 3339: 3309: 3308: 3304: 3282: 3281: 3277: 3247: 3240: 3239: 3235: 3204: 3203: 3199: 3153: 3152: 3148: 3118: 3117: 3110: 3088: 3087: 3083: 3070:(12): 456–463. 3061: 3060: 3056: 3048: 3041: 3038: 3029: 3028: 3021: 2991: 2984: 2977: 2976: 2972: 2938: 2937: 2933: 2911: 2910: 2906: 2876: 2875: 2871: 2837: 2836: 2832: 2806: 2805: 2798: 2776: 2775: 2771: 2741: 2740: 2736: 2714: 2713: 2709: 2694: 2681: 2680: 2676: 2646: 2645: 2641: 2578: 2575: 2574: 2573: 2571: 2569: 2563: 2562: 2558: 2551: 2528: 2527: 2523: 2489: 2488: 2484: 2459: 2455: 2450: 2428: 2415: 2411: 2402: 2398: 2394: 2391:Wilhelm Schlenk 2387:Arthur Lapworth 2379: 2199:petroleum ether 2161: 2139: 2132: 2117: 2104: 2100: 2096: 2093: 2089: 2087:tricyanomethane 2083: 2079: 2075: 2073:trinitromethane 2069: 2061: 2060: 2053: 2046: 2039: 2037: 2026: 2019: 2015: 1982: 1978: 1974: 1970: 1932: 1928: 1924: 1920: 1899: 1895: 1891: 1887: 1866: 1862: 1858: 1854: 1833: 1829: 1825: 1821: 1799: 1795: 1753: 1749: 1745: 1741: 1720: 1716: 1712: 1708: 1687: 1683: 1679: 1658: 1654: 1650: 1646:Cyclopentadiene 1629: 1625: 1621: 1600: 1596: 1592: 1570: 1566: 1562: 1541: 1537: 1515: 1511: 1507: 1485: 1481: 1477: 1456: 1452: 1448: 1444:Phenylacetylene 1426: 1422: 1418: 1395: 1391: 1387: 1366: 1362: 1341: 1337: 1333: 1312: 1308: 1304: 1300: 1277: 1273: 1252: 1248: 1244: 1240:Diphenylmethane 1222: 1218: 1214: 1193: 1189: 1185: 1181: 1160: 1156: 1134: 1130: 1126: 1122: 1101: 1097: 1093: 1072: 1068: 1064: 1043: 1039: 1018: 1014: 1010: 999: 977: 969: 962: 948:in DMSO is 18. 947: 940: 932:cyclopentadiene 925: 918: 911: 903: 892: 882: 875: 862: 860: 853: 826: 784: 771: 767: 756:cyclopentadiene 744: 740: 736: 732: 728: 724: 720: 716: 712: 697: 693: 691: 685:from toluene (p 680: 677: 676: 674: 671: 667: 663: 661: 652: 648: 639: 635: 624: 620: 618: 548: 544: 522: 518: 514: 510: 506: 502: 498: 494: 490: 486: 482: 478: 470: 466: 462: 461:, isopropanide 456: 453: 452: 450: 446: 441: 436: 432: 426: 418: 415: 414: 412: 409: 405: 397: 393: 383: 380: 379: 377: 361: 357: 353: 346: 342: 285: 276: 272: 268: 264: 260: 184: 136:carbonyl groups 123:, and alkynyl ( 69: 65: 61: 28: 23: 22: 15: 12: 11: 5: 3595: 3593: 3585: 3584: 3579: 3569: 3568: 3565: 3564: 3557: 3551: 3544: 3536: 3535:External links 3533: 3530: 3529: 3508:(2): 211–214. 3488: 3461: 3430: 3399: 3380:(4): 914–923. 3364: 3337: 3326:(4): 862–865. 3302: 3275: 3245: 3233: 3214:(2): 391–395. 3197: 3146: 3108: 3081: 3054: 3051:on 2019-07-02. 3036: 3019: 3000:(6): 690–695. 2989: 2982: 2970: 2931: 2904: 2869: 2850:(1): 274–275. 2830: 2796: 2769: 2734: 2707: 2692: 2674: 2639: 2592:(2): 410–413. 2576: 2567: 2556: 2549: 2521: 2502:(9): 819–822. 2482: 2452: 2451: 2449: 2446: 2445: 2444: 2439: 2434: 2427: 2424: 2378: 2375: 2322: 2321: 2303: 2302: 2264: 2263: 2226: 2225: 2160: 2157: 2149:aldol reaction 2137: 2130: 2120:Triflidic acid 2115: 2067: 2059: 2058: 2051: 2044: 2035: 2024: 2020:The reported p 2012: 2011: 2010: 2009: 2008: 2007: 1999: 1998: 1995: 1994: 1991: 1984: 1968: 1966:Triflidic acid 1962: 1961: 1958: 1955: 1952: 1945: 1944: 1941: 1934: 1918: 1912: 1911: 1908: 1901: 1885: 1883:Meldrum's acid 1879: 1878: 1875: 1868: 1852: 1846: 1845: 1842: 1835: 1819: 1813: 1812: 1809: 1802: 1793: 1786: 1785: 1782: 1775: 1772: 1766: 1765: 1762: 1755: 1739: 1733: 1732: 1729: 1722: 1706: 1700: 1699: 1696: 1689: 1677: 1671: 1670: 1667: 1660: 1648: 1642: 1641: 1638: 1631: 1619: 1613: 1612: 1609: 1602: 1590: 1584: 1583: 1580: 1573: 1560: 1554: 1553: 1550: 1543: 1535: 1529: 1528: 1525: 1518: 1505: 1499: 1498: 1495: 1488: 1475: 1469: 1468: 1465: 1458: 1446: 1440: 1439: 1436: 1429: 1416: 1409: 1408: 1405: 1398: 1385: 1379: 1378: 1375: 1368: 1360: 1354: 1353: 1350: 1343: 1331: 1325: 1324: 1321: 1314: 1298: 1291: 1290: 1287: 1280: 1271: 1265: 1264: 1261: 1254: 1242: 1236: 1235: 1232: 1225: 1212: 1206: 1205: 1202: 1195: 1179: 1173: 1172: 1169: 1162: 1154: 1147: 1146: 1143: 1136: 1120: 1114: 1113: 1110: 1103: 1091: 1085: 1084: 1081: 1074: 1062: 1056: 1055: 1052: 1045: 1037: 1031: 1030: 1027: 1020: 1008: 1002: 1001: 997: 991: 988: 985: 975: 960: 945: 938: 923: 916: 909: 901: 890: 880: 873: 858: 851: 824: 783: 780: 689: 659: 616: 599: 598: 546: 542: 442:point group). 439: 424: 365:retrosynthetic 316: 315: 306:of the anion. 302:the extent of 300: 284: 281: 183: 180: 73: 72: 51:conjugate base 26: 24: 14: 13: 10: 9: 6: 4: 3: 2: 3594: 3583: 3580: 3578: 3575: 3574: 3572: 3563: 3556: 3552: 3550: 3543: 3539: 3538: 3534: 3525: 3521: 3516: 3511: 3507: 3503: 3499: 3492: 3489: 3484: 3480: 3476: 3472: 3465: 3462: 3457: 3453: 3449: 3445: 3441: 3434: 3431: 3426: 3422: 3418: 3414: 3410: 3403: 3400: 3395: 3391: 3387: 3383: 3379: 3375: 3368: 3365: 3360: 3356: 3352: 3348: 3341: 3338: 3333: 3329: 3325: 3321: 3317: 3313: 3306: 3303: 3298: 3294: 3290: 3286: 3279: 3276: 3271: 3267: 3263: 3259: 3255: 3251: 3244: 3237: 3234: 3229: 3225: 3221: 3217: 3213: 3209: 3201: 3198: 3193: 3189: 3185: 3181: 3177: 3173: 3169: 3165: 3161: 3157: 3150: 3147: 3142: 3138: 3134: 3130: 3126: 3122: 3115: 3113: 3109: 3104: 3100: 3096: 3092: 3085: 3082: 3077: 3073: 3069: 3065: 3058: 3055: 3047: 3040: 3035: 3026: 3024: 3020: 3015: 3011: 3007: 3003: 2999: 2995: 2988: 2981: 2974: 2971: 2966: 2962: 2958: 2954: 2950: 2946: 2942: 2935: 2932: 2927: 2923: 2919: 2915: 2908: 2905: 2900: 2896: 2892: 2888: 2884: 2880: 2873: 2870: 2865: 2861: 2857: 2853: 2849: 2845: 2841: 2834: 2831: 2826: 2822: 2818: 2814: 2810: 2803: 2801: 2797: 2792: 2788: 2784: 2780: 2773: 2770: 2765: 2761: 2757: 2753: 2749: 2745: 2738: 2735: 2730: 2726: 2722: 2718: 2711: 2708: 2703: 2699: 2695: 2693:9780080438504 2689: 2685: 2678: 2675: 2670: 2666: 2662: 2658: 2654: 2650: 2643: 2640: 2635: 2631: 2626: 2621: 2617: 2613: 2608: 2603: 2599: 2595: 2591: 2587: 2583: 2560: 2557: 2552: 2546: 2542: 2538: 2534: 2533: 2525: 2522: 2517: 2513: 2509: 2505: 2501: 2497: 2493: 2486: 2483: 2480: 2476: 2472: 2468: 2467: 2462: 2457: 2454: 2447: 2443: 2442:Nitrile anion 2440: 2438: 2435: 2433: 2430: 2429: 2425: 2423: 2422: 2421:carbonium ion 2418: 2408: 2392: 2388: 2384: 2376: 2374: 2372: 2371:Mosher's acid 2368: 2364: 2360: 2357: 2353: 2350: 2346: 2342: 2338: 2334: 2330: 2327: 2317: 2312: 2308: 2307: 2306: 2297: 2293: 2292: 2291: 2289: 2285: 2281: 2277: 2273: 2269: 2258: 2254: 2253: 2252: 2250: 2246: 2242: 2241:carboxylation 2238: 2234: 2232: 2220: 2216: 2215: 2214: 2212: 2208: 2204: 2200: 2196: 2195:-butyllithium 2194: 2188: 2186: 2185:organolithium 2182: 2178: 2174: 2170: 2166: 2158: 2156: 2154: 2150: 2146: 2141: 2136: 2129: 2125: 2121: 2114: 2110: 2109:fulminic acid 2088: 2074: 2066: 2050: 2043: 2034: 2030: 2023: 2017: 2014: 2003: 2002: 2001: 2000: 1992: 1989: 1985: 1969: 1967: 1964: 1963: 1959: 1956: 1953: 1950: 1947: 1946: 1942: 1939: 1935: 1919: 1917: 1914: 1913: 1909: 1906: 1902: 1886: 1884: 1881: 1880: 1876: 1873: 1869: 1853: 1851: 1848: 1847: 1843: 1840: 1836: 1820: 1818: 1817:Malononitrile 1815: 1814: 1810: 1807: 1803: 1794: 1791: 1788: 1787: 1783: 1780: 1776: 1773: 1771: 1768: 1767: 1763: 1760: 1756: 1740: 1738: 1737:Acetylacetone 1735: 1734: 1730: 1727: 1723: 1707: 1705: 1702: 1701: 1697: 1694: 1690: 1678: 1676: 1673: 1672: 1668: 1665: 1661: 1649: 1647: 1644: 1643: 1639: 1636: 1632: 1620: 1618: 1615: 1614: 1610: 1607: 1603: 1591: 1589: 1586: 1585: 1581: 1578: 1574: 1561: 1559: 1556: 1555: 1551: 1548: 1544: 1536: 1534: 1531: 1530: 1526: 1523: 1519: 1506: 1504: 1501: 1500: 1496: 1493: 1489: 1476: 1474: 1471: 1470: 1466: 1463: 1459: 1447: 1445: 1442: 1441: 1437: 1434: 1430: 1417: 1414: 1411: 1410: 1406: 1403: 1399: 1386: 1384: 1381: 1380: 1376: 1373: 1369: 1361: 1359: 1356: 1355: 1351: 1348: 1344: 1332: 1330: 1327: 1326: 1322: 1319: 1315: 1299: 1296: 1293: 1292: 1288: 1285: 1281: 1272: 1270: 1267: 1266: 1262: 1259: 1255: 1243: 1241: 1238: 1237: 1233: 1230: 1226: 1213: 1211: 1208: 1207: 1203: 1200: 1196: 1180: 1178: 1175: 1174: 1170: 1167: 1163: 1155: 1152: 1149: 1148: 1144: 1141: 1137: 1121: 1119: 1116: 1115: 1111: 1108: 1104: 1092: 1090: 1087: 1086: 1082: 1079: 1075: 1063: 1061: 1058: 1057: 1053: 1050: 1046: 1038: 1036: 1033: 1032: 1028: 1025: 1021: 1009: 1007: 1004: 1003: 996: 992: 989: 986: 983: 982: 974: 967: 963: 959: 951: 950: 949: 944: 937: 933: 929: 922: 915: 908: 900: 896: 889: 884: 879: 872: 868: 857: 850: 846: 844: 838: 837:-butyllithium 836: 831: 827: 823: 817: 816:Brønsted acid 813: 809: 805: 801: 797: 793: 792:mineral acids 789: 781: 779: 777: 776:organolithium 765: 761: 757: 753: 748: 710: 705: 703: 688: 658: 645: 633: 629: 615: 611: 607: 606:-butyllithium 605: 593: 589: 588: 587: 585: 581: 580:-butyllithium 579: 574: 570: 567: 563: 558: 556: 552: 540: 536: 532: 528: 476: 443: 430: 403: 391: 375: 369: 366: 351: 340: 335: 333: 329: 328:pyrophoricity 323: 321: 313: 309: 305: 301: 298: 294: 293: 292: 290: 282: 280: 258: 254: 250: 246: 241: 233: 229: 224: 216: 212: 211:carbocations. 209: 205: 201: 197: 193: 189: 181: 179: 176: 172: 168: 164: 160: 159:proton donors 156: 152: 150: 145: 144:iminium salts 141: 137: 133: 132:electrophiles 128: 126: 122: 118: 114: 110: 106: 102: 98: 94: 90: 86: 82: 81:deprotonation 78: 60: 59: 58: 56: 52: 47: 45: 41: 37: 33: 19: 3554: 3541: 3505: 3501: 3491: 3474: 3470: 3464: 3447: 3443: 3433: 3416: 3412: 3402: 3377: 3373: 3367: 3350: 3346: 3340: 3323: 3319: 3315: 3311: 3305: 3291:(10): 4842. 3288: 3284: 3278: 3253: 3249: 3242: 3236: 3211: 3207: 3200: 3159: 3155: 3149: 3124: 3120: 3094: 3090: 3084: 3067: 3063: 3057: 3046:the original 3033: 2997: 2993: 2992:of Water?". 2986: 2979: 2973: 2948: 2944: 2934: 2917: 2913: 2907: 2882: 2878: 2872: 2847: 2843: 2833: 2816: 2812: 2782: 2778: 2772: 2747: 2743: 2737: 2720: 2716: 2710: 2683: 2677: 2652: 2648: 2642: 2589: 2585: 2559: 2531: 2524: 2499: 2495: 2485: 2464: 2456: 2380: 2358: 2351: 2340: 2328: 2323: 2315: 2304: 2279: 2275: 2271: 2267: 2265: 2248: 2244: 2236: 2230: 2227: 2192: 2189: 2177:racemization 2162: 2142: 2134: 2127: 2112: 2064: 2062: 2048: 2041: 2032: 2029:acetonitrile 2021: 2016: 1675:Nitromethane 1473:Thioxanthene 1269:Acetonitrile 994: 972: 957: 942: 935: 920: 913: 906: 898: 887: 885: 877: 870: 866: 855: 848: 842: 834: 821: 787: 785: 782:Carbon acids 749: 706: 686: 656: 644:bond lengths 613: 603: 600: 577: 559: 474: 444: 370: 354:MeMg(Br)(OEt 339:butyllithium 336: 324: 317: 289:nucleophilic 286: 252: 248: 244: 239: 237: 231: 227: 199: 185: 148: 129: 74: 54: 48: 35: 29: 3477:(9): 3838. 3450:(2): 1664. 3419:: 694–705. 3121:Tetrahedron 3032:"Chem 206 p 2432:Carbocation 2349:phosphorane 2187:compounds. 1790:Acetic acid 1558:Benzoxazole 1006:Cyclohexane 876:(BH) > p 804:acetic acid 796:nitric acid 788:carbon acid 692:in DMSO of 662:in DMSO of 626:= 30.6) in 619:in DMSO of 566:crown ether 527:cyclopropyl 312:aromaticity 304:conjugation 240:delocalized 204:Bent's rule 115:, alkenyl ( 55:carbon acid 3571:Categories 2448:References 2399:C][NMe 2047:= 0.98 × p 1533:Chloroform 1358:Fluoroform 841:potassium 752:proton NMR 741:][PhCH 729:][PhCH 632:12-crown-4 584:12-crown-4 477:-butanide 343:[BuLi] 273:C=C=CH ↔ H 66:CH + B → R 18:Carbanions 3141:0040-4020 2965:2199-3793 2951:(2): 15. 2945:ChemTexts 2864:1099-0682 2669:0002-7863 2516:0040-4039 2471:carbanion 2393:prepared 2333:deuterium 2326:phosphate 2173:chirality 2163:With the 928:hydroxide 845:-butoxide 812:Arrhenius 778:species. 717:][CPh 649:[CHPh 539:phenethyl 535:neopentyl 429:inversion 374:methanide 238:However, 200:localized 196:lone pair 125:acetylide 99:carbon), 91:carbon), 42:in which 36:carbanion 3524:98171271 3394:17243828 3270:19275192 3228:21166439 3192:29697201 3184:27115918 2899:12203352 2819:: 1–20. 2764:12203352 2702:55939535 2634:16592384 2437:Enolates 2426:See also 2284:methanol 2145:carbonyl 1957:HCl (g) 1850:Dimedone 1588:Fluorene 1383:Xanthene 1177:Dithiane 1000:in DMSO 987:Formula 737:[NMe 725:[NMe 713:[NMe 636:[CPh 551:benzylic 332:cyanides 245:slightly 182:Geometry 155:diiodine 3164:Bibcode 3002:Bibcode 2594:Bibcode 2395:[Ph 2377:History 2356:alcohol 2337:stannyl 2274:-bromo- 2203:dry ice 2124:triflyl 1951:(Cl–H) 1503:Acetone 1413:Ethanol 1295:Aniline 1151:Ammonia 1118:Toluene 1089:Propene 1060:Benzene 1035:Methane 978:values. 808:benzene 709:Schlenk 601:Adding 555:allylic 251:) and ( 186:Absent 157:), and 107:(at an 105:alkynes 95:(at an 93:alkenes 87:(at an 85:alkanes 3577:Anions 3522:  3392:  3314:- and 3268:  3226:  3190:  3182:  3139:  3039:Table" 2963:  2897:  2862:  2762:  2700:  2690:  2667:  2632:  2625:392297 2622:  2614:  2547:  2514:  2233:isomer 2107:, and 2090:HC(CN) 2054:+ 11.6 1993:~ −16 1792:(O–H) 1617:Indene 1415:(O–H) 1297:(N–H) 1153:(N–H) 473:, and 402:ketene 376:anion 277:C−C≡CH 140:imines 101:arenes 70:C + HB 44:carbon 38:is an 3520:S2CID 3316:trans 3188:S2CID 3049:(PDF) 3042:(PDF) 2920:(6). 2616:66197 2612:JSTOR 2461:IUPAC 2409:and 2249:trans 2076:HC(NO 1971:HC(SO 1960:−2.0 1877:10.3 1844:11.1 1811:12.6 1784:12.9 1764:13.3 1731:16.4 1698:17.2 1669:18.0 1640:20.1 1611:22.6 1582:24.4 1552:24.4 1527:26.5 1497:28.6 1467:28.8 1438:29.8 1407:30.0 1377:30.5 1352:30.6 1323:30.6 1289:31.3 1263:32.3 1234:35.1 984:Name 802:like 798:, or 794:like 562:Power 531:cubyl 348:) or 117:vinyl 113:alkyl 53:of a 40:anion 3562:Link 3549:Link 3390:PMID 3266:PMID 3224:PMID 3180:PMID 3137:ISSN 2961:ISSN 2895:PMID 2860:ISSN 2760:PMID 2698:OCLC 2688:ISBN 2665:ISSN 2630:PMID 2570:and 2545:ISBN 2512:ISSN 2324:The 2151:and 2101:(CN) 1954:HCl 1943:2.3 1925:CCO) 1910:7.3 1800:COOH 1774:HCN 1746:CCO) 1538:CHCl 1204:~39 1171:~41 1145:~43 1112:~44 1083:~49 1054:~56 1029:~60 966:DMSO 839:and 770:and 723:and 675:PhCH 621:CHPh 582:and 569:salt 553:and 545:→ σ* 537:and 529:and 295:the 265:C=CH 230:and 173:and 153:and 121:aryl 77:base 34:, a 3510:doi 3479:doi 3452:doi 3421:doi 3382:doi 3378:129 3355:doi 3328:doi 3312:cis 3293:doi 3258:doi 3216:doi 3172:doi 3160:120 3129:doi 3099:doi 3072:doi 3010:doi 2953:doi 2922:doi 2887:doi 2852:doi 2821:doi 2817:372 2787:doi 2752:doi 2725:doi 2721:107 2657:doi 2653:100 2620:PMC 2602:doi 2537:doi 2504:doi 2475:doi 2473:". 2416:CNa 2373:.) 2347:to 2245:cis 2231:cis 2197:in 2027:in 1363:CHF 1215:(CH 964:in 628:THF 608:to 547:C–C 515:(CH 511:CH• 503:(CH 479:(CH 463:(CH 433:•CH 406:•CH 394:•CH 392:of 165:in 119:), 83:of 30:In 3573:: 3518:. 3506:69 3504:. 3500:. 3475:55 3473:. 3448:47 3446:. 3417:91 3415:. 3411:. 3388:. 3376:. 3351:86 3349:. 3324:83 3322:. 3289:72 3287:. 3264:. 3254:74 3252:. 3222:. 3212:76 3210:. 3186:. 3178:. 3170:. 3158:. 3135:. 3125:54 3123:. 3111:^ 3095:96 3093:. 3068:21 3066:. 3022:^ 3008:. 2998:94 2996:. 2959:. 2947:. 2943:. 2918:76 2916:. 2893:. 2881:. 2858:. 2848:50 2846:. 2815:. 2799:^ 2783:96 2781:. 2758:. 2746:. 2719:. 2696:. 2663:. 2651:. 2628:. 2618:. 2610:. 2600:. 2590:74 2588:. 2584:. 2572:CH 2543:. 2510:. 2500:22 2498:. 2494:. 2463:, 2412:Ph 2290:: 2270:)- 2155:. 2085:, 1975:CF 1929:CH 1921:(F 1861:12 1796:CH 1750:CH 1742:(H 1715:12 1684:NO 1680:CH 1599:10 1595:13 1571:NO 1484:10 1480:13 1427:OH 1394:10 1390:13 1340:16 1336:19 1309:NH 1278:CN 1274:CH 1251:12 1247:13 1223:SO 1157:NH 1131:CH 1040:CH 1017:12 772:Li 768:Li 698:Ph 694:CH 668:Ph 664:CH 612:(p 575:, 523:C• 513:, 501:, 495:CH 491:CH 471:CH 451:CH 447:CH 440:3h 425:3v 413:CH 378:CH 192:sp 138:, 109:sp 97:sp 89:sp 57:: 3558:a 3555:K 3545:a 3542:K 3526:. 3512:: 3485:. 3481:: 3458:. 3454:: 3427:. 3423:: 3396:. 3384:: 3361:. 3357:: 3334:. 3330:: 3299:. 3295:: 3272:. 3260:: 3246:a 3243:K 3230:. 3218:: 3194:. 3174:: 3166:: 3143:. 3131:: 3105:. 3101:: 3078:. 3074:: 3037:a 3034:K 3016:. 3012:: 3004:: 2990:a 2987:K 2983:a 2980:K 2967:. 2955:: 2949:6 2928:. 2924:: 2901:. 2889:: 2883:8 2866:. 2854:: 2827:. 2823:: 2793:. 2789:: 2766:. 2754:: 2748:8 2731:. 2727:: 2704:. 2671:. 2659:: 2636:. 2604:: 2596:: 2582:" 2577:3 2568:3 2553:. 2539:: 2518:. 2506:: 2477:: 2414:3 2403:] 2401:4 2397:3 2359:4 2352:3 2341:2 2329:1 2316:i 2280:n 2276:l 2272:l 2268:S 2237:s 2193:s 2138:a 2135:K 2131:a 2128:K 2116:a 2113:K 2105:H 2103:5 2099:5 2097:C 2092:3 2082:3 2080:) 2078:2 2068:a 2065:K 2056:. 2052:a 2049:K 2045:a 2042:K 2040:p 2036:a 2033:K 2025:a 2022:K 1981:3 1979:) 1977:3 1973:2 1931:2 1927:2 1923:3 1898:4 1896:O 1894:8 1892:H 1890:6 1888:C 1865:2 1863:O 1859:H 1857:8 1855:C 1832:2 1830:N 1828:2 1826:H 1824:3 1822:C 1798:3 1752:2 1748:2 1744:3 1719:4 1717:O 1713:H 1711:7 1709:C 1686:2 1682:3 1657:6 1655:H 1653:5 1651:C 1628:8 1626:H 1624:9 1622:C 1597:H 1593:C 1569:5 1567:H 1565:7 1563:C 1540:3 1516:O 1514:6 1512:H 1510:3 1508:C 1486:S 1482:H 1478:C 1455:6 1453:H 1451:8 1449:C 1425:5 1423:H 1421:2 1419:C 1396:O 1392:H 1388:C 1365:3 1338:H 1334:C 1311:2 1307:5 1305:H 1303:6 1301:C 1276:3 1249:H 1245:C 1221:2 1219:) 1217:3 1192:2 1190:S 1188:8 1186:H 1184:4 1182:C 1159:3 1133:3 1129:5 1127:H 1125:6 1123:C 1100:6 1098:H 1096:3 1094:C 1071:6 1069:H 1067:6 1065:C 1042:4 1015:H 1013:6 1011:C 998:a 995:K 993:p 976:a 973:K 968:. 961:a 958:K 956:p 946:a 943:K 939:a 936:K 924:a 921:K 917:a 914:K 910:a 907:K 905:p 902:a 899:K 891:a 888:K 881:a 878:K 874:a 871:K 867:K 863:B 859:a 856:K 852:a 849:K 843:t 835:n 832:( 825:a 822:K 820:p 745:] 743:2 739:4 733:] 731:2 727:4 721:] 719:3 715:4 696:3 690:a 687:K 681:2 678:− 670:2 666:2 660:a 657:K 653:] 651:2 647:( 640:] 638:3 623:3 617:a 614:K 604:n 578:n 543:C 521:3 519:) 517:3 509:2 507:) 505:3 499:• 497:2 493:3 487:C 485:3 483:) 481:3 475:t 469:2 467:) 465:3 457:2 454:− 449:3 435:3 419:3 416:− 408:3 396:3 384:3 381:− 360:2 358:) 356:2 345:6 314:. 275:2 271:2 269:H 263:2 261:H 253:Z 249:E 232:Z 228:E 149:N 142:/ 68:3 64:3 62:R 20:)

Index

Carbanions
organic chemistry
anion
carbon
conjugate base
base
deprotonation
alkanes
sp
alkenes
sp
arenes
alkynes
sp
alkyl
vinyl
aryl
acetylide
electrophiles
carbonyl groups
imines
iminium salts
N-bromosuccinimide
diiodine
proton donors
reactive intermediates
organic chemistry
organolithium reagents
Grignard reagents
π delocalization

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