Bond Dissociation Energies

Transcript

1 Bond Dissociation Energies Yu-Ran Luo The bond dissociation energy (enthalpy) is also referred to as bond disruption energy, bond energy, bond strength, or binding energy (abbreviation: BDE, BE, or D). It is defined as the standard enthalpy change of the following fission: R X R + X. The BDE, denoted by D o (R X), is usually derived by the thermochemical equation, D o (R X) = f H o (R) + f H o (X) f H o (RX). The enthalpy of formation f H o of a large number of atoms, free radicals, ions, clusters and compounds is available from the websites of NIST, NASA, CODATA, and IUPAC. Most authors prefer to use the BDE values at K. The following seven tables provide essential information of experimental BDE values of R X and R + X bonds. (1) Table 1: Bond Dissociation Energies in Diatomic Molecules (2) Table 2: Enthalpy of Formation of Gaseous Atoms (3) Table 3: Bond Dissociation Energies in Polyatomic Molecules (4) Table 4: Enthalpies of Formation of Free Radicals and Other Transient Species (5) Table 5: Bond Dissociation Energies of Common Organic Molecules (6) Table 6: Bond Dissociation Energies in Diatomic Cations (7) Table 7: Bond Dissociation Energies in Polyatomic Cations The data in these tables have been revised through September TABLE 1. Bond Dissociation Energies in Diatomic Molecules The BDEs in diatomic species have usually been measured by spectroscopy or mass spectrometry. In the absence of data on the enthalpy function, the values at 0 K, D o (A B), are converted to D o by the approximate equation: 298 D o 298 (A B) Do (A B) + (3/2)RT = D o (A B) kj mol 1 This table has been arranged in an alphabetical order of the atoms A in the diatomics A B. Ac O Ag Ag ± Ag Al ± Ag Au ± Ag Bi 192 ± 42 1 Ag Br ± Ag Cl ± Ag Cu ± Ag D Ag Dy 130 ± 19 1 Ag Eu 127 ± 13 1 Ag F ± Ag Ga 159 ± 17 1 Ag Ge ± 21 1 Ag 02.4 ± Ag Ho 124 ± 19 1 Ag I 234 ± 29 1 Ag In ± Ag Li Ag Mn 99.2 ± 21 1 Ag Na ± Ag Nd <213 1 Ag 21 ± 21 1 Ag S ± Ag Se ± Ag Si ± Ag Sn 136 ± 21 1 Ag Te ± Al Al ± Al Ar Al As ± Al Au ± Al Br ± Al Al Ca Al Cl Al Co ± Al Cr ± Al Cu ± Al D Al F Al 88 ± 13 1 Al I ± Al Kr Al Li Al N 368 ± 15 1 Al Ne Al Ni ± Al O ± Al P ± Al Pd ± Al S 332 ± 10 1 Al Sb ± 6 1 Al Se 318 ± 13 1 Al Si ± Al Te 268 ± 13 1 Al Ti Al U 326 ± 29 1 Al V ± Al Xe Am O 553 ± 36 1 Ar Ar Ar B Ar Br ~5.0 1 Ar Ar Ca 4.44 ± Ar Cd 5.57 ± Ar Ga Ar Ge <5.4 1 Ar He Ar Hg Ar I ~5.3 1 Ar In Ar Kr Ar Li ~ Ar Mg ~3.7 1 Ar Na ~4.2 1 Ar Ne Ar Si Ar Sn <5.1 1 Ar Tl Ar Xe Ar Zn As As ± As Cl As D As F As Ga ± As 74.0 ± As I ± 24 1 As In 201 ± 10 1 As N 489 ± As O 484 ± 8 1 As P ± As S ± As Sb ± As Se 96 1 As Tl ± Au Au ± Au B ± Au Ba ± Au Be ± Au Bi 293 ± Au Br 213 ± K11100_S09.indb 65 2/23/10 5:28:50 PM

2 9-66 Bond Dissociation Energies Au Ca ± Au Ce 322 ± 18 1 Au Cl 280 ± 13 1 Au Co ± Au Cr ± Au Cs 253 ± Au Cu ± Au D Au Dy 259 ± 24 1 Au Eu 245 ± 12 1 Au F Au Fe ± Au Ga 290 ± 15 1 Au Ge ± Au 00.5 ± Au Ho 267 ± 35 1 Au I Au In ± Au La 457 ± 28 1 Au Li ± Au Lu 332 ± 19 1 Au Mg ± Au Mn ± 21 1 Au Na ± Au Nd 294 ± 29 1 Au Ni 247 ± Au 23 ± 21 1 Au Pb 133 ± 42 1 Au Pd ± 21 1 Au Pr 311 ± 25 1 Au Rb 243 ± Au Rh ± 29 1 Au S ± Au Sc 280 ± 40 1 Au Se ± Au Si ± Au Sn ± Au Sr 264 ± 42 1 Au Tb 285 ± 33 1 Au Te ± Au U 318 ± 29 1 Au V ± Au Y 310 ± 12 1 B B B Br ± B 48 ± 29 1 B Cd B Ce 305 ± 21 1 B Cl B D ± B F B 45.2 ± B I B Ir ± 17 1 B La 335 ± 63 1 B N ± B Ne B O B P 347 ± B Pd ± B Pt ± B Rh ± 21 1 B Ru ± 21 1 B S 577 ± B Sc 272 ± 63 1 B Se 462 ± B Si 317 ± 12 1 B Te 354 ± 20 1 B Th 297 ± 33 1 B Ti 272 ± 63 1 B U 322 ± 33 1 B Y 289 ± 63 1 Ba Br Ba Cl Ba D Ba Ba H Ba I ± Ba O 562 ± Ba Pd ± Ba Rh ± 25 1 Ba S 418 ± 21 1 Be Be 59 1 Be Br Be Cl Be D Be 73 1 Be 21 1 Be I Be O Be S 372 ± 59 1 Be T Bi Bi Bi Br Bi Cl ± Bi D Bi F ± Bi Ga ± Bi H Bi I ± Bi In ± Bi Li Bi O ± Bi P ± 13 1 Bi Pb ± Bi S ± Bi Sb ± Bi Se ± Bi Sn 193 ± 13 1 Bi Te ± Bi Tl ± Bk O Br Br ± Br 18.0 ± Br Ca Br Cd 159 ± 96 1 Br Ce Br Cl ± Br Co 326 ± 42 1 Br Cr ± Br Cs ± Br Cu 331 ± 25 1 Br D Br Dy ± Br Er Br Eu Br F 280 ± 12 1 Br Fe 243 ± 84 1 Br Ga 402 ± 13 1 Br Gd Br Ge 347 ± 8 1 Br ± Br Hg Br Ho Br I ± Br In 409 ± 10 1 Br K ± Br La Br Li ± Br Lu Br Mg Br Mn ± Br Mo Br N ± 21 1 Br Na ± Br Nd Br Ni 360 ± 13 1 Br 37.6 ± Br P Br Pb ± Br Pr Br Rb ± Br S 218 ± 17 1 Br Sb 314 ± 59 1 Br Sc 444 ± 63 1 Br Se 297 ± 84 1 Br Si ± Br Sm Br Sn 337 ± 13 1 Br Sr Br T Br Tb Br Th Br Ti Br Tl 331 ± 21 1 Br Tm Br U 377 ± 15 1 Br V 439 ± 42 1 Br W Br Xe 5.94 ± Br Y 481 ± 84 1 Br Yb Br Zn 138 ± 29 1 Br Zr C 18.3 ± C Ce 443 ± 30 1 C Cl ± C D C 13.8 ± C Fe ± C Ge ± 11 1 C 38.4 ± C Hf 540 ± 25 1 C I ± C Ir 631 ± 5 1 C La 463 ± 20 1 C Mo 482 ± 16 1 C N ± C Nb ± C Ni C O ± C Os 608 ± 25 1 C P ± C Pd 436 ± 20 1 C Pt ± C Rh 580 ± 4 1 C Ru 648 ± 13 1 C S ± C Sc 444 ± 21 1 C Se ± C Si C Tc 564 ± 29 1 C Th 453 ± 17 1 C Ti 423 ± 30 1 K11100_S09.indb 66 2/23/10 5:28:52 PM

3 Bond Dissociation Energies 9-67 C U 455 ± 15 1 C V 423 ± 24 1 C Y 418 ± 14 1 C Zr ± Ca Ca ± Ca Cl 409 ± Ca D Ca 29 1 Ca Ca I ± Ca Kr 5.15 ± Ca Li 84.9 ± Ca O ± Ca Pd Ca S 335 ± 21 1 Ca Xe 7.31 ± Cd Cd Cd Cl Cd F 305 ± 21 1 Cd 9.0 ± Cd I 97.2 ± Cd In Cd K Cd Kr Cd Na Cd Ne Cd 36 ± 84 1 Cd S ± Cd Se ± Cd Te ± Cd Xe Ce Ce Ce Cl Ce 82 ± 42 1 Ce I Ce Ir 575 ± 9 1 Ce N 519 ± 21 1 Ce O Ce Os 524 ± 20 1 Ce Pd 319 ± 21 1 Ce Pt 550 ± 5 1 Ce Rh 545 ± 7 1 Ce Ru 494 ± 12 1 Ce S Ce Se ± Ce Te ± Cf O Cl Cl ± Cl Co Cl Cr Cl Cs ± Cl Cu ± Cl D ± Cl Dy Cl Er Cl Eu Cl F Cl Fe Cl Ga 463 ± 13 1 Cl Gd Cl Ge ± Cl ± Cl Hg 92.0 ± Cl Ho Cl I ± Cl In 436 ± 8 1 Cl K ± Cl La Cl Li 469 ± 13 1 Cl Lu ± 2 1 Cl Mg Cl Mn Cl N ± Cl Na ± Cl Nd Cl Ni Cl ± Cl P Cl Pb 301 ± 50 1 Cl Pr Cl Ra 343 ± 75 1 Cl Rb ± Cl S Cl Sb 360 ± 50 1 Cl Sc Cl Se Cl Si ± Cl Sm Cl Sn 350 ± 8 1 Cl Sr Cl T Cl Ta Cl Tb Cl Th Cl Ti ± Cl Tl ± Cl Tm Cl U Cl V 477 ± 63 1 Cl W Cl Xe Cl Y 523 ± 84 1 Cl Yb Cl Zn 229 ± 8 1 Cl Zr Cm O 710 ± Co Co <127 1 Co Cu ± Co D ± Co F 431 ± 63 1 Co Ge 230 ± 21 1 Co 44.9 ± Co I 280 ± 21 1 Co Mn 50 ± 8 1 Co Nb ± Co O ± Co S Co Sc Co Si ± 17 1 Co Ti ± Co Y ± Co Zr ± Cr Cr ± 6 1 Cr Cu ± Cr 23 ± 19 1 Cr Fe ~75 1 Cr Ge 154 ± 7 1 Cr H ± Cr I ± Cr N ± Cr Nb ± Cr O 461 ± Cr Pb 105 ± 2 1 Cr S Cr Sn 141 ± 3 1 Cs Cs ± Cs 17.1 ± Cs H Cs Hg 8 1 Cs I ± Cs Li 72.9 ± Cs Na 63.2 ± Cs 93 ± 25 1 Cs Rb ± Cu Cu Cu D Cu Dy 144 ± 18 1 Cu F Cu Ga ± 15 1 Cu Ge ± 21 1 Cu 54.8 ± 6 1 Cu Ho 144 ± 19 1 Cu I 289 ± 63 1 Cu In ± Cu Li Cu Na ± Cu Ni ± Cu 87.4 ± Cu S ± Cu Se ± Cu Si ± Cu Sn 170 ± 10 1 Cu Tb 191 ± 18 1 Cu Te ± D D ± D ± D Ga < D Ge D ± D Hg D I D In D K D Li D Lu D Mg ± D Mn 312 ± 6 1 D N D Ni D O D P D Pt D S ± D Si D Sr D T D Tl D Zn Dy Dy Dy 31 1 Dy I ± Dy O Dy S 414 ± 42 1 Dy Se 322 ± 20 1 Dy Te 234 ± 20 1 Er Er 75 ± 29 1 Er 65 ± 17 1 Er I Er O Er S 418 ± 21 1 Er Se 326 ± 20 1 Er Te 238 ± 20 1 Es O Eu Eu K11100_S09.indb 67 2/23/10 5:28:54 PM

4 9-68 Bond Dissociation Energies Eu 44 1 Eu I Eu Li ± Eu O Eu Rh 238 ± 34 1 Eu S ± Eu Se ± Eu Te ± F F ± F Fe F Ga 584 ± 13 1 F Gd 590 ± 17 1 F Ge 523 ± 13 1 F ± F Hf 650 ± 15 1 F Hg ~180 1 F Ho F I F In 516 ± 13 1 F K F Kr F La ± F Li 577 ± 21 1 F Lu 405 ± 19 1 F Mg F Mn ± F Mo F N F Na F Nd ± F Ni ± F Np 430 ± 50 1 F 20 1 F P F Pb 355 ± 13 1 F Pr 582 ± 46 1 F Pu 538 ± 29 1 F Rb 494 ± 21 1 F Ru F S ± F Sb 439 ± 96 1 F Sc ± F Se 339 ± 42 1 F Si ± 17 1 F Sm F Sn 476 ± 8 1 F Sr F T ± F Ta 573 ± 13 1 F Tb 561 ± 42 1 F Th F Ti 569 ± 33 1 F Tl 439 ± 21 1 F Tm F U F V 590 ± 63 1 F W F Xe F Y ± F Yb ± F Zn 364 ± 63 1 F Zr ± Fe Fe Fe Ge ± 29 1 Fe H 148 ± 3 1 Fe I Fe O ± Fe S ± Fe Si 297 ± 25 1 Fm O Ga Ga < Ga 65.9 ± Ga I 334 ± 13 1 Ga In 94.0 ± 3 1 Ga Kr Ga Li ± Ga O 374 ± 21 1 Ga P ± Ga Sb ± Ga Te 265 ± 21 1 Ga Xe Gd Gd ± Gd I Gd O Gd S ± Gd Se 430 ± 15 1 Gd Te 341 ± 15 1 Ge Ge ± Ge 63.2 ± Ge I 268 ± 25 1 Ge Ni ± Ge O ± Ge Pb ± Ge Pd ± Ge S 534 ± 3 1 Ge Sc 270 ± 11 1 Ge Se ± Ge Si Ge Sn ± 13 1 Ge Te ± Ge Y 279 ± 11 1 H ± H Hg H I ± H In H K H Li ± H Mg ± H Mn 251 ± 5 1 H Mo ± H N H Na ± H Nb >221.9 ± H Ni 240 ± 8 1 H O ± H P ± H Pb H Pd 234 ± 25 1 H Pt H Rb H Rh ± H Ru 223 ± 15 1 H S ± H Sb ± H Sc 205 ± 17 1 H Se H Si ± H Sn 264 ± 17 1 H Sr 164 ± 8 1 H T H Te ± H Ti ± H Tl ± 4 1 H V ± H Yb ± H Zn 85.8 ± 2 1 He He He Hg He Xe Hf Hf 328 ± 58 1 Hf N 535 ± 30 1 Hf O 801 ± 13 1 Hg Hg 8.10 ± Hg I ± Hg K Hg Kr Hg Li ± Hg Na Hg Ne Hg 69 1 Hg Rb Hg S ± Hg Se ± Hg T Hg Te <142 1 Hg Tl Hg Xe Hg Zn Ho Ho Ho I Ho O Ho S ± Ho Se 333 ± 15 1 Ho Te 259 ± 15 1 I I ± I In ± I K ± I Kr I La I Li ± I Lu I Mg I Mn ± I Mo I N 159 ± 17 1 I Na ± I Nd I Ni 293 ± 21 1 I 33.4 ± I Pb 194 ± 38 1 I Pr I Rb ± I Si ± I Sm I Sn 235 ± 3 1 I Sr I Tb I Te 192 ± 42 1 I Th 361 ± 25 1 I Ti I Tl 285 ± 21 1 I Tm I U 299 ± 27 1 I Xe ~6.9 1 I Y ± I Yb I Zn ± I Zr In In 82.0 ± In Kr In Li 92.5 ± In O 346 ± 30 1 In P ± In S ± K11100_S09.indb 68 2/23/10 5:28:56 PM

5 Bond Dissociation Energies 9-69 In Sb ± In Se ± In Te ± In Xe In Zn Ir Ir 361 ± 68 1 Ir La 577 ± 12 1 Ir Nb 465 ± 25 1 Ir O 414 ± 42 1 Ir Si ± 21 1 Ir Th 574 ± 42 1 Ir Ti 422 ± 13 1 Ir Y 457 ± 15 1 K K K Kr K Li 82.0 ± K Na ± K Zn K 71.5 ± K Rb ± K Xe Kr Kr Kr Li ~ Kr Mg 6.71 ± Kr Na ~ Kr Ne Kr O <8 1 Kr Tl Kr Xe Kr Zn La La La N 519 ± 42 1 La O La Pt 505 ± 12 1 La Rh 550 ± 12 1 La S ± La Se ± La Te ± 15 1 La Y 197 ± 21 1 Li Li Li Mg 67.4 ± Li Na ± Li O ± Li Pb 78.7 ± 8 1 Li S ± Li Sb ± Li Si Li Sm ± Li Tm ± Li Xe ~ Li Yb ± Lr O Lu Lu 142 ± 33 1 Lu O Lu Pt 402 ± 34 1 Lu S ± Lu Se 418 ± 15 1 Lu Te 325 ± 15 1 Md O Mg Mg Mg Ne ~4.1 1 Mg O ± Mg S Mg Xe 9.70 ± Mn Mn 61.6 ± Mn O 362 ± 25 1 Mn S 301 ± 17 1 Mn Se ± Mo Mo ± Mo Nb 452 ± 25 1 Mo O N N ± N O ± N P ± N Pt ± N Pu 469 ± 63 1 N S 467 ± 24 1 N Sb 460 ± 84 1 N Sc 464 ± 84 1 N Si ± N Ta 607 ± 84 1 N Th 577 ± 33 1 N Ti 476 ± 33 1 N U 531 ± 21 1 N V 523 ± 38 1 N Xe N Y 477 ± 63 1 N Zr 565 ± 25 1 Na Na ± Na Ne ~3.8 1 Na 70 ± 4 1 Na Rb ± Na Xe ~ Nb Nb Nb Ni ± Nb O ± Nb Ti ± Nb V ± Nd Nd Nd O Nd S ± Nd Se Nd Te 305 ± 15 1 Ne Ne Ne Xe Ne Zn Ni Ni Ni O 366 ± 30 1 Ni Pd Ni Pt ± Ni S 356 ± 21 1 Ni Si 318 ± 17 1 Ni V ± Ni Y ± Ni Zr ± No 68 1 Np O O O ± O Os O P O Pa O Pb ± O Pd ± O Pr O Pt ± O Pu O Rb 276 ± O Re 627 ± 84 1 O Rh 405 ± 42 1 O Ru 528 ± 42 1 O S ± O Sb 434 ± 42 1 O Sc ± O Se ± O Si ± O Sm O Sn O Sr ± O Ta O Tb O Tc O Te 377 ± 21 1 O Th O Ti ± O Tl 213 ± 84 1 O Tm O U O V O W 720 ± 71 1 O Xe O Y ± O Yb ± 10 1 O Zn O Zr ± Os Os 415 ± 77 1 P P P Pt ± P Rh ± P S 442 ± 10 1 P Sb ± P Se ± P Si P Te ± P Th 372 ± 29 1 P Tl 209 ± 13 1 P U 293 ± 21 1 P W 305 ± 4 1 Pb Pb 86.6 ± Pb S Pb Sb ± Pb Se ± Pb Si ± Pb Te ± Pd Pd >136 1 Pd Pt Pd Si 261 ± 12 1 Pd Y 241 ± 15 1 Po Po Pr Pr Pr S ± Pr Se ± Pr Te 326 ± 20 1 Pt Pt ± Pt Si 501 ± 18 1 Pt Th 551 ± 42 1 Pt Ti ± Pt Y 474 ± 12 1 Rb Rb ± Re Re 432 ± 30 1 Rh Rh ± Rh Sc 444 ± 11 1 Rh Si ± Rh Th 513 ± 21 1 Rh Ti ± Rh U 519 ± 17 1 Rh V 364 ± 29 1 Rh Y 446 ± 11 1 Ru Ru ± Ru Si ± 21 1 Ru Th 592 ± 42 1 Ru V 414 ± 29 1 S S S Sb S Sc ± K11100_S09.indb 69 2/23/10 5:28:58 PM

6 9-70 Bond Dissociation Energies A B D o 298 /kj mol 1 Ref. A B D o 298 /kj mol 1 Ref. A B D o 298 /kj mol 1 Ref. A B D o 298 /kj mol 1 Ref. S Se ± Sb Tl ± Si Te Ti Ti S Si 617 ± 5 1 Sc Sc 163 ± 21 1 Si Y 258 ± 17 1 Ti V ± S-Sm S Sn S Sr ± S Ta ± S Tb 515 ± 42 1 S Te 335 ± 42 1 S Ti 418 ± 3 1 S Tm 368 ± 21 1 S U ± S V ± S Y ± S Yb S Zn ± S Zr ± Sb Sb ± Sb Te ± Sc Se 385 ± 17 1 Sc Si ± 14 1 Sc Te 289 ± 17 1 Se Se Se Si 538 ± 13 1 Se Sm ± Se Sn ± Se Sr ± Se Tb 423 ± 20 1 Se Te Se Ti 381 ± 42 1 Se Tm 274 ± 40 1 Se V 347 ± 21 1 Se Y 435 ± 13 1 Se Zn ± Si Si Sm Sm 54 ± 21 1 Sm Te ± Sn Sn ± Sn Te ± Sr Sr ± T T Ta Ta 390 ± 96 1 Tb Tb Tb Te 339 ± 42 1 Tc Tc Te Te ± Te Ti 289 ± 17 1 Te Tm 182 ± 40 1 Te Y 339 ± 13 1 Te Zn ± Th Th 289 ± 33 1 Ti Zr ± Tl Tl Tl Xe Tm Tm 54 ± 17 1 U U 222 ± 21 1 V V ± V Zr ± W W Xe Xe Y Y ~270 ± 39 1 Yb Yb Zn Zn 22.2 ± Zr Zr ± References 1. Luo, Y. R. Comprehensive Handbook of Chemical Bond Energies, CRC Press, Boca Raton, FL, Hildenbrand, D. L., and Lau, K.H., J. Phys. Chem. A 110, 11886, Chattopadhyaya, S., Pramanik, A., Banerjee, A., and Das, K. K., J. Phys. Chem. A 110, 12303, Brutti, S., Balducci, G., and Gigli, G., Rapid Commun. Mass Spectrom. 21, 89, Staanum, P., Pashov, A., Knöckel, H., and Tiemann, E., Phys. Rev. A 75, , Ciccioli, A., Gigli, G., Meloni, G., and Testani, E., J. Chem. Phys. 127, /1, Nagarajan, R., and Morse, M. D., J. Chem. Phys. 127, /1, Li, J., Hao, Y., Yang, J., Zhou, C., and Mo, Y., J. Chem. Phys. 127, /1, Armentrout, P. B., Organometallics 26, 5473, Shayesteh, A., Henderson, R. D. E., Le Roy, R. J., and Bernath, P. F., J. Phys. Chem. A 111, 12495, Hildenbrand, D. H., J. Phys. Chem. A 112, 3813, Dooley, K. S., Geidosch, J. N., and North, S. W., Chem. Phys. Lett. 457, 303, Citir, M., Metz, R. B., Belau, L., and Ahmed, M., J. Phys. Chem. A 112, 9584, Hildenbrand, D. L., Lau, K. H., Perez-Mariano, J., and Sanjurjo, A., J. Phys. Chem. A 112, 9978, Gibson, J. K., Haire, R. G., Santos, M., Pires de Matos, A., and Marçalo, J., J. Phys. Chem. A 112, 11373, TABLE 2. Enthalpy of Formation of Gaseous Atoms Atom f H o 298 /kj mol 1 Ref. Atom f H o 298 /kj mol 1 Ref. Atom f H o 298 /kj mol 1 Ref. Atom f H o 298 /kj mol 1 Ref. Ac Ag ± Al ± Am As ± 13 1 Au ± B 565 ± 5 2 Ba ± Be 324 ± 5 2 Bi ± Bk Br ± ± Ca ± Cd ± Ce ± Cf Cl ± Cm Co Cr ± Cs 76.5 ± Cu ± Dy ± Er ± Es Eu ± F ± Fe ± Ga ± Gd ± Ge 372 ± ± Hf ± Hg ± Ho ± I ± In 243 ± 4 1 Ir 669 ± 4 1 K 89.0 ± La ± Li ± Lu ± Mg ± Mn ± Mo ± N ± Na ± Nb ± 8 3 Nd ± Ni ± Np ± Os 787 ± P ± Pa Pb ± Pd ± Pr ± Pt ± Pu Ra Rb 80.9 ± Re 774 ± Rh 556 ± 4 1 Ru ± S ± Sb ± Sc ± 4 1 Se ± 4 1 Si ± 8 2 Sm ± Sn ± Sr ± Ta ± Tb ± Tc Te ± Th 602 ± 6 2 Ti 473 ± 3 2 K11100_S09.indb 70 2/23/10 5:29:00 PM

7 Bond Dissociation Energies 9-71 Atom f H o 298 /kj mol 1 Ref. Tl ± Tm ± Atom f H o 298 /kj mol 1 Ref. U 533 ± 8 2 V ± 8 3 Atom f H o 298 /kj mol 1 Ref. W ± Y ± Atom f H o /kj 298 mol 1 Ref. Yb ± Zn ± Zr ± References 1. Brewer, L., and Rosenblatt, G. M., Adv. High Temp. Chem. 2, 1, Cox, J. D., Wagman, D. D., and Medvedev, V. A., Eds., CODATA Key Values for Thermodynamics, Hemisphere Publishing Corporation, New York, 1989; updated e-version: 3. NIST Chemistry WebBook, NIST-JANAF Thermochemical Table, 4th Edn., Chase, Jr., M. W., Ed., ACS, AIP, New York, Chandrasekharaiah, M.S., and Gingerich, K.A., Thermodynamic properties of gaseous species, in Handbook on the Chemistry and Physics of Rare Earths, Gschneidner, Jr., K.A., and Ering, L., Eds., Elsevier, Amsterdam, 1989, Vol. 12, Chap. 86, pp Lias, S.G., Bartmess, J. E., Liebman, J. F., Holmes, J. L., Levin, R. D., and Mallard, W. G., J. Phys. Chem. Ref. Data 17, Suppl. 1, Kleinschmidt, P.D., Ward, J. W., Matlack, G. M., and Haire, R. G., High Temp. Sci. 19, 267, Ruscic, B., Pinzon, R.E., Morton, M. E., Srinivasan, N. K., Su, M.-C., Sutherland, J. W., and Michael, J. V., J. Phys. Chem. A 110, 6592, TABLE 3. Bond Dissociation Energies in Polyatomic Molecules The D o values in polyatomic molecules are notoriously difficult to measure accurately since the mechanism of the kinetic systems 298 involved in many of the measurements are seldom straightforward. Thus, much lively controversy has taken place in the literature and is likely to continue for some time to come. We will continue updating and presenting our assessment of the most reliable BDE data every year. The references relating to each of the D o values listed in Table 3 are contained in the Comprehensive Handbook of Chemical Bond 298 Energies, by Yu-Ran Luo, CRC Press, Many D o in Table 3 are derived from the equation 298 D o 298 (R-X) = f Ho (R) + f H o (X) f H o (RX) Here, the enthalpies of formation of the atoms and radicals are taken from Tables 2 and 4, respectively, and the enthalpies of formation of the molecules are from reference sources listed in the above Comprehensive Handbook of Chemical Bond Energies. Table 3 presents H-C, C-C, C-halogen, O-, N-, S-, Si-, Ge-, Sn-, Pb-, P-, As-, Sb-, Bi-, Se-, Te-, and metal-x BDEs. The boldface in the species indicates the dissociated fragment. The metal-x BDEs are arranged on the basis of the Periodic Table with the new IUPAC notation for Groups 1 to 18, see inside front cover of this Handbook. (1) C H BDEs 39.3 ± ± ± ± ± ( CH 19.2 ± ( C 00.4 ± ( C 19.7 ± ( )CH( ( ( )CH( ± CH( )CH( ± ( ( ) HCC ± HCCCC 39 ± 12 1 CHC 84.1 ± CC HCC =CHCC CC ± HCC ± HCCCH( ± CCCH( ± HCCCCCC H ~543 ± 13 1 C=CH 64.2 ± =C=CH 71.1 ± CH=CH =CH 69 ± 3 1 =CH =CH =C( ) =CHCH=CH ± ( =CH CH 20.5 ± =CH =CHCH( ± =C( ) 56.1 ± ( =CH C( ) H-cyclo ± H- -cyclo ± H-cyclo ± H-cyclo ± H-cyclo H ± H ± H CH( ) ± H CH( ± H CH( -p-oh ± H C( ± H C( ± H-C ± H-C ± H ± H CHF ± H F ± H CClF ± H CCl 2 F ± H CBrF ± H CHClF ± H ± H CHCl ± H Cl ± H CFClBr 413 ± 21 1 K11100_S09.indb 71 2/23/10 5:29:01 PM

8 9-72 Bond Dissociation Energies H CHClBr ± H CCl 2 Br 387 ± 21 1 H CClBr ± 21 1 H CBr ± H CHBr ± H Br ± H CI ± 29 1 H CHI ± H I ± CF ± CHF 2 CF ± FCF ± CHF 2 CFH 26.8 ± ± CF ± FCHF 13.4 ± CHF ± F 33.5 ± CHF 10.9 ± CHCl 25.9 ± CClBr 04.2 ± CClF 2 CHF 12.1 ± CCl ± CHCl 2 CCl ± CCl ± CHCl 06.6 ± Cl 23.1 ± CBr ± Br 15.1 ± CHBr 15.0 ± CF 2 =CF 64.4 ± CF 2 CF CHCl 07.0 ± =CH-CHF 70.7 ± =CHCHCl 70.7 ± =CHCHBr 74.0 ± H H O01.92 ± CHO67 ± 11 1 O01.2 ± O21.7 ± 8 1 O92 1 O94.6 ± O06.3 ± ( CHO83.7 ± ( CHO94.6 ± =CH O41.4 ± ( CO18.4 ± ( =CH CHO Ph 2 CHO26 1 CH(OH ~385 1 Bond D o 298 /kj mol 1 Ref. ( OH HO ( (OH)CH H O CHF 2 O ± CHF 2 OCHF ± O ± O ( COC( O Ot-C( OPh H-2-oxiran-2-yl ± H-tetrahydrofuran-2-yl ± HC(O) ± FC(O) C(O) 74.0 ± C(O) C(O) =CHC(O) C(O) iso- C(O) C(O) ( CH C(O) CH( )C(O) tert-buc(o) Et 2 CHC(O) ( ) 8 C(O) C(O) 71.1 ± Ph C(O) PhC( C(O) H CH=C=O C(O)94.5 ± C(O)Cl C(O) CO ± C(O) CO MeCO Me ± EtCO Me ± CO ± Me COPh H C(O)O C(O)O98.7 ± Cl C(O)O H C(O)O ± C(O)O ± C(O)O C(O)O C(O)OPh ± C(O)OEt Ph C(O)OEt Me 2 CHC(O)OEt PhCHMe(C(O)OEt H-furaylmethyl ± N ± N= ± N ± N ± N ± N ± HO N ± ( N70.7 ± ( N79.9 ± ( N84.5 ± ( N ± ( N ± (( C N ± (Bu N (npr81 ± (( CH N ± ( CHN ± NH ± ( N ± tert-bun( ± ((HO ( ))N ± (HO N ± ((HO )CH( ) N ± Ph N PhN( ± Ph 2 N ± PhN( Ph ± N( Ph ± PhN( CH= ± N( CH= ± NNH( ) HNN( ( N ± H CN ± CN ± CN ± Ph CN CN (CN (CN)(N ( CHCN N89.1 ± H HCNN ± H CNN 331 ± 17 1 N N N Me 2 CHN C(N )CH K11100_S09.indb 72 2/23/10 5:29:04 PM

9 Bond Dissociation Energies 9-73 H C(S)99.6 ± S92.9 ± S ± PhS Ph SPh (PhS CHPh PhSCHPh SO S S S Ph Ph S Me Ph S Ph S tbu Ph 2 CHS Ph (SPh H SiMe ± H C( SiMe ± 5 1 H SiMe 2 Ph H CH(( Si 397 ± 13 1 H B(RO H CH(( P 385 ± 13 1 (2) C C BDEs ± ± ± iso ± ± iso ± sec ± tert ± ± CH( ± C( ( 60.9 ± H ± ± ± iso- iso ± ± iso- iso ± sec- sec ± tert- tert ± cyclo ± cyclo ± cyclo- cyclo ± C 20.5 ± C C ± CH( )C 05.4 ± CH( )C C ± C( C 95.8 ± C( C C ± Bond D o 298 /kj mol 1 Ref. CH ± CH=C ± cyclopro-en-1-yl ± CH= ± C( )= ± CH( )CH= ± C( CH= ± cyclo ± ± HCC ± ± ± CH( ) ± C( ± CHCHPh CH( ± C( )( ± ± ± ± CH( ± C( ± Ph 2 CH CHPh ± Ph CPh ± R-R, π-dimer, R = phenalenyl R-R, σ-dimer, R = phenalenyl R-R, R = 9- phenylfluorenyl ± CHF ± CClF ± F ± ± CHBrCl ± Br ± I ± ± CHF 2 CHF ± CClF 2 CClF ± CF 2 Cl CFCl ± CHF 2 F ± F F ± CHF ± F ± CHClF ± CF 2 Br CHClF CF 2 Br ± ± CClF ± CHCl ± Cl ± ± CHCl 2 CHCl ± CHCl 2 Cl ± CHCl ± CHBrCl CHClBr CHClBr ± Cl Cl ± Cl ± Br 3 C ± Br 3 C CBr ± CHBr Br Cl Br Br ± I I ± Br ± I ± CF ± CF=CF Cl ± CHCl ± Cl CHCl ± Cl CCl ± CCl ± Br CHBr ± Cl CHCl ± Cl CCl ± CHBr CHBr ± ± ± ± CHPh ± CPh ± CF 2 CF CFCF ± F CPh ± CHF 2 CPh ± O64.8 ± O05.4 ± O56.9 ± O57.3 ± iso- O54.8 ± O55.6 ± sec- O52.7 ± iso- O54.0 ± O13.4 ± HO C O58.2 ± N O35.6 ± O ± K11100_S09.indb 73 2/23/10 5:29:06 PM

10 9-74 Bond Dissociation Energies O O ± C(O)54.8 ± C(O)09.2 ± C(O)F ± C(O)Cl ± C(O)Cl ± CHCl 2 C(O)Cl ± CCl C(O)Cl ± C(O)08.4 ± C(O)Cl ± C(O) ± C(O) ± C(O) ± iso- C(O) ± C(O) ± tert- C(O) ± C(O) ± C(O) ± HC(O) C(O)95.8 ± ClC(O) C(O)Cl ± C(O) C(O)02.5 ± C(O) C(O) ± C(O) C(O) ± C(O)O84.9 ± C(O)O70.7 ± C(O)O10.5 ± CCl C(O)O57.7 ± Br C(O)O58.2 ± N C(O)O49.4 ± NH C(O)O00.4 ± C(O)O29.7 ± C(O)O70.0 ± HO C(O)O71.5 ± HOC(O) C(O)O34.7 ± NH C(O)O01.2 ± CH(N ) C(O)O31.4 ± N C(O)O25.5 ± CN CN ± HC(O) CN ± HC(S) CN ± CN ± CN ± NCC CN CN ± CN ± CN ± CH( )CN ± C( CN ± C( )(CN) (Ph (CN)C C(CN)(Ph (N C C(N ± (3) C halogen BDEs F CN F ± F CHF ± F F ± F CF 2 Cl F CFCl ± F CHFCl ± F ± 4 1 F Cl ± F ± F C C F C C19 ± 21 1 F CF=CF ± F CF ± F F CF ± F ± F ± F ± F iso ± F tert ± F ± F 485 ± 25 1 F ± F CO97.9 ± F CO F COCl F C(O) ± Cl CN ± Cl ± Cl CHF ± 8 1 Cl F ± Cl CF 2 Cl ± Cl CFCl ± Cl CHFCl ± Cl Cl CHCl ± Cl Cl ± Cl CBrCl ± Cl Br ± Cl I ± Cl ± Cl C CCl 443 ± 50 1 Cl C C35.6 ± Cl CN Cl CCl=CCl Cl CH= ± Cl CF=CF ± Cl CF ± Cl CF 2 CF 2 Cl ± Cl CCl Cl CCl Cl CHCl ± Cl CCl 2 CHCl Cl CHCl ± Cl Cl ± Cl CHBr ± Cl ± Cl CH= ± Cl ± Cl Cl Cl iso ± Cl CHCH= Cl ± Cl sec ± Cl tert ± CHCHCl( 00.0 ± Cl ± Cl C( ( 52.7 ± Cl cyclo ± Cl ± Cl ± Cl ± Cl C(O)Cl ± Cl COF Cl C(O) ± Cl C(O) ± Cl C(O) ± Cl C(O) Cl C(O)O10.9 ± Cl C(O)O Cl C(N Br CN ± Br ± Br CHF ± Br CF 2 Cl ± Br ± Br Cl ± Br CBr ± Br CHBr ± Br Br ± Br I ± Br ± Br C C Br CH= ± Br CF ± Br CClBr ± Br CF 2 CF 2 Br ± Br CHCl ± Br CF ± K11100_S09.indb 74 2/23/10 5:29:09 PM

11 Bond Dissociation Energies 9-75 Br Cl ± Br CHCl ± Br ± Br CH= ± Br ± Br iso ± Br Br Br CF 2 CF ± CFBr ± Br ± Br sec ± Br tert ± Br ± Br ~328 1 Br ± Br ± Br 1 C Br 2 C Br anthracenyl Br C(O) ± Br C(O) ± Br C(O) ± Br C(O) Br C(O)O57.4 ± Br C(N I CN I ± I 168 ± 42 1 I Cl ± I Br ± I I ± I ± I CN ± I CF ± I CF 2 CF 2 I ± I ± I CHFCClF ± 2 1 I CF ± I-CFICH ± CFI I CH= ± I ± I CH= ± I ± I iso ± I F I tert ± I ± I < I ± I 1-naphthyl ± I 2-naphthyl ± I CN ± I O ± I S ± I C(O) ± I C(O) ± I C(O)OH ± I C(N (4) O X BDEs HO ± FO ClO BrO 05 1 IO O 40.2 ± 3 1 O HC CO O 41.0 ± =CHO O 47.7 ± O H 433 ± 2 1 iso- O 42.3 ± O sec- O 41.4 ± tert- O 44.9 ± tert-bu O O 42.7 ± C(OH)O 46.9 ± ( C(OH)O 50.6 ± HC(O)O 68.6 ± C(O)O 68.6 ± C(O)O iso- C(O)O C(O)O 64.4 ± HOO ± OO 70.3 ± OO 83 1 FOO 79 1 OO 86 1 CHCl 2 OO 83 1 ClOO 79 1 CBr 3 OO 83 1 BrOO 79 1 OO 54.8 ± CHClOO 77 1 CCl 2 OO 83 1 CHClOO 84 1 Cl 5 OO 83 1 iso- OO 56 1 =CH OO tert- OO 52.3 ± Bond D o 298 /kj mol 1 Ref. OO 84 1 OO 63 1 ( CHOO 70 1 C(O)OO 86 1 CCl 2 (CN)OO 84 1 OH OO 68 1 H ONO H OON H ON H ON H ONNOH H OP ± H OS O41.4 ± H OSiMe ( )CHNO ( CNO ( )CHNO PhO 62.8 ± α-tocopherol RO β-tocopherol RO γ-tocopherol RO δ-tocopherol RO p- - O O HO O10.66 ± HO OF ± HO OCl ~146 1 HO OBr ± FO OF ClO OCl 72.4 ± IO OI 74.9 ± 17 1 trans-perp-ho ONO 67.8 ± cis-cis-ho ONO 83.3 ± HO ON ± HO O ± HO O ± HO O ± HO O-iso ± HO O-tert ± HO OC(O) ± HO OC(O) ± O O ± O O ± O O O O ± iso- O O-iso sec- O O-sec ± tert-buo O-tert-Bu ± tert-bu O O - tert-bu EtC(Me O OC(Me Et ± ( CO OC( ± K11100_S09.indb 75 2/23/10 5:29:11 PM

12 9-76 Bond Dissociation Energies Bond D o 298 /kj mol 1 Ref. Ph 3 CO OCPh S O OS S O OOS ( CO OSi( tert-buo OGeEt tert-buo OSnEt OO O ± HC(O)O OH ± FC(O)O OC(O)F C(O)O ON ± C(O)O OC(O) ± 21 1 C(O)O OC(O) OC(O)O OC(O)F ± OC(O)O O ± OC(O)O OC(O) O C(O)O OC(O) C(O)O OC(O) FS(O O-OS(O F HO ± FO 408 ± 17 1 HO ± HO ± HO ± HO CH= ± HO ± HO iso ± HO ± HO sec ± HO iso ± HO tert ± HO CH( )(n 98.3 ± HO CH( ± HO C( ( 95.8 ± HO ± HO ± HO ± HO C( ± cyclo- O85.8 ± C 10 O68.6 ± C 10 O67.8 ± ( (N )C O10.4 ± C(O)-O59.4 ± HO -O O ± I O ± O ± O CHCl ± O ± O iso ± O ± O-tert ± O ± CH( ) O ± O ± OC(O)83.7 ± HC(O) O57.7 ± C(O) O59.4 ± C(O) O47.7 ± HO C(O)O68.2 ± OC(O) ± HC(O) O ± C(O) O ± C(O) O ± C(O) O ± O O ± C(O) OC(O) ± C(O) OC(O) ± OO00.4 ± OO32.2 ± OO iso- OO tert- OO09.2 ± OO ± OO ± OO ± OO CClF 2 OO CCl 2 F-OO Cl OO ± CHCl 2 OO ± OO 92.0 ± HC(O) OO C(O) OOC(O) ClO ± ON ON ON49.4 ± iso- ON54.4 ± ON56.5 ± iso- ON54.0 ± sec- ON53.6 ± tert- ON52.7 ± ( )( C ON54.0 ± ON ON O CN O N ± O NO ± O N NO NO 40.6 ± Bond D o 298 /kj mol 1 Ref. N ON 95.4 ± cis-ho N trans-ho-n00.64 ± FO NO ± 17 1 cis-clo NO ± trans-clo NO ± cis-bro NO ± trans-bro NO ± trans-perp-hoo NO ± 4 1 O NO ± O NO ± O NO ± iso- O NO ± O NO ± iso- O NO ± sec- O NO ± tert- O NO ± tert-amo NO ± O NO HO N FO N ± ClO N BrO N ± IO N ~100 1 O N ± O N ± O N ± iso- O N ± HOO N 99.2 ± OO N 86.6 ± OO N CF 2 ClOO N CFCl 2 OO N OO N N(O)-O ± N(O)-O 392 ± 8 1 N-64.9 ± N=N(O)( )-O ± (O)N=N(O)( )- O ± O SO O SOF O SOCl O S(OH ± 25 1 HO S93.3 ± HO SO13.4 ± HO S(OH) ± HO S ± HO S ± F O F OF K11100_S09.indb 76 2/23/10 5:29:13 PM

13 Bond Dissociation Energies 9-77 F O ± F O > F ON Cl O Cl OCl Cl O ± Cl O Cl O-tert Cl OOCl Cl ON Br O09.6 ± Br OBr Br O-tert Br ON ± I O I OI I-ON > (5) N X BDEs H N ± H NF ± H NN H N H N= 364 ± 25 1 H NO H NHO41 1 H NCO ± H NCS ± H NCS ± N ± tert-bun ± N ( N95.8 ± H NHNH( 76 ± 21 1 H NHN( 356 ± 21 1 N CN (N C=O (N C=S CSN PhCSN (PhNH C=S (N C=N Ph 2 C=N H N(SiMe H ΝΗPh NHO92 1 NH(CONMe H ΝPh HN N ON N ± ON NO 8.49 ± ON N N N 57.3 ± 1 1 N N ± F 2 N NF ± N NH ± N N( ± N NH ± N N NN( ) NO ( N-NO N ± N ± N ± N13.0 ± N13.4 ± iso- N23.0 ± tert- N99.6 ± NC N NO NO NO NO CH NO iso- NO ± tert- NO N26.8 ± N11.3 ± NO N ± N N iso- N N sec- N tert- N N ± N ± (N ) N (N C N NF NF ± N ± N ± N ± iso- N ± N ± sec- N ± iso- N ± tert- N ± pyridin-2-yl N N ± N ± CH(CH N ± HC(O) N ± C(O) N ± HS NO S NO ± tert-bus NO Ph S NO S-NO 81.2 ± SCN SCN FS NF F N F N F NF F N Cl NO ± Cl N ± Cl NF 2 ~134 1 Cl N Br NO ± Br N 82.0 ± Br NF 2 < I NO 75.6 ± 4 1 I N 79.6 ± 4 1 (6) S X BDEs H S81.18 ± H S ± H SCH ± H S H S H S-iso ± H S-tert ± H SO30.5 ± H SCO H SCOPh H S H SS ± H SPh ± H SS18.0 ± H SSS92.9 ± HS S70.7 ± FS SF ClS SCl HS S HS SPh ± S S ± S S MeS SPh ± S S ± S S 305 ± 21 1 K11100_S09.indb 77 2/23/10 5:29:15 PM

14 9-78 Bond Dissociation Energies HS ± HS ± HS ± HS iso ± HS ± HS sec ± HS iso ± HS tert ± HS ± HS ± HS C(O)09.6 ± HS C(O) ± S ± HOS ± SO ± HOS ± S S 392 ± 43 1 F S F S (F79 1 Cl S <272 1 Cl S Cl-S Ph Br-SBr 259 ± 17 1 Br S <230 1 I-S06.7 ± I-S ± (7) Si-, Ge-, Sn-, and Pb X BDEs Si 83.7 ± Me 3 Si 96 ± 7 1 Si 2 73 ± 8 1 ( Si 96 ± 4 1 Si 82 ± 5 1 ( S Si (iprs Si PhMe 2 Si 77 ± 7 1 Ph 2 SiH 79 ± 7 1 Ph 2 MeSi 61 ± 10 1 SiF 3 32 ± 5 1 SiCl SiBr 3 34 ± 8 1 Si Si 321 ± 4 1 Si Si ± 8 1 Ph 3 Si SiPh F 3 Si SiF ± 25 1 Si 375 ± 5 1 SiF Si NO ± Si P Si F 638 ± 5 1 Si Cl 458 ± 7 1 Si Br 376 ± 9 1 Si I 299 ± 8 1 Ge 48.9 ± Me 3 Ge Ph 3 Ge ( Ge-Ge( ( Ge Me 3 Sn Ph 3 Sn ( Sn-Sn( ( Sn-Cl 425 ± 17 1 ( Pb-Pb( Cl 3 Pb-Cl 271 ± 84 1 ( Pb- 238 ± 21 1 (8) P-, As-, Sb-, Bi X BDEs P 51.0 ± PH 22.2 ± P P ( P P( F 2 P 49 1 Cl 2 P Cl 356 ± 8 1 Br 2 P Br <259 1 I 2 P I P Si As 19.2 ± Sb-88.3 ± F 2 Bi F 435 ± 19 1 Br 2 Bi Br > (9) Se- and Te X BDEs H Se34.93 ± H Se ± PhSe SePh 280 ± 19 1 H Te77.0 ± H Te PhTe TePh ± (10) Metal-Centered BDEs Arranged by the Periodic Table (10.1) Group 1 Li O Li ± Li n ± Na O Na <200 1 K O59 1 Rb O56.2 ± Cs O73 1 (10.2) Group 2 BeO 69 1 Be(OH) O76 1 MgO 41 1 Mg(OH) O49 1 BrMg BrMg BrMg i BrMg t BrMg BrMg BrMg C( Ca(OH) O09 1 Sr(OH) O07 1 Ba(OH) O43 1 (10.3) Group 3 Sc 116 ± 29 1 Sc La CH(SiMe ± Nd CH(SiMe ± Sm 26.8 ± Sm O Sm (η 3 - ) ± Sm S-n ± Sm N( ± Sm SiH (SiMe ± 21 1 Sm P(Et ± Eu I ± Yb I ± Lu CH(SiMe ± SiMe 3 Th 77 ± 6 1 SiMe 3 Th O 371 ± 24 1 Th 375 ± 9 1 Th Si( 369 ± 12 1 (C 9 Th 342 ± 9 1 tbu U 49.7 ± SiMe 3 U 53.7 ± [HB(3,5-Me 2 Pz ] U(Cl Cl SiMe 3 U I ± tbu U O 307 ± 9 1 SiMe 3 U CO 43.1 ± (C 9 U ± U(Cl) 358 ± 11 1 SiMe 3 U THF 41.0 ± (10.4) Group 4 Ti Cl Ti(Cl) Cl Ti I K11100_S09.indb 78 2/23/10 5:29:18 PM

15 Bond Dissociation Energies 9-79 Bond D o 298 /kj mol 1 Ref. Ti CO Ti(CO) CO Ti 174 ± 29 1 Ti(Cl) Ti(Cl)( Ti( ) Zr 51.0 ± Zr(H) 26.4 ± 4 1 Zr Cl Zr Br Zr(I) I ± Zr (Ph) O82.4 ± Zr (Ph)(OH) OH ± Zr(η 5 - (N )H N ± Zr 276 ± 10 1 Zr ( ) 300 ± 10 1 Zr (Si(SiMe 3 ) SiMe ± 30 1 Hf(H) 46.0 ± Hf )( ) 274 ± 10 1 (10.5) Group 5 )(CO V η 2 90 ± 20 1 )(CO V CO 146 ± 21 1 V 169 ± 18 1 V V( ) Nb TFE 18.8 ± Ta( ) ± 5 1 (Me 3 Si ) 4 Ta ( SiMe 3 ) ± (10.6) Group 6 [Cr(CO )] 2 Hg [Cr(CO )] Hg Cr(CO) 5 Xe 37.7 ± (CO (PPh 3 )(η 5 - )Cr H ± )Cr(CO H, Cr(CO) 5 78 ± 4 1 (P( (CO Cr 30.5 ± (η 6 - )(CO Cr 251 ± 17 1 Cr(CO) 5 N 2 81 ± 4 1 (P( (CO Cr N ± )(CO Cr SH Cr(CO) 5 CO ± Cr(CO) 5 C ~33.5 ± 8 1 Cr 9.6 ± Cr( ) ± Cr(CO) ± (P( (CO Cr P(OMe ± ))Mo(CO 90 1 Mo 46 1 Mo(H) 56.9 ± Mo(CO ) I ± Mo 72 1 (P( (CO Mo 27.2 ± (P( (CO Mo N ± Mo(CO) 5 CO ± Mo(CO ) 203 ± 8 1 W(CO) 5 Xe 35.1 ± W(CO ) 03 1 W(H) 10.9 ± W(I) 73 ± 14 1 (CO) 5 W 67 1 (P( )(CO W (η 2 - ) 28.5 ± W(CO) 5 CO ± W( ) ± 4 1 (10.7) Group 7 F 3 Mn MnF ± (CO) 5 Mn Mn(CO) ± 8 1 (CO) 5 Mn (PPh 3 )Mn(CO) MnBr(CO) 4 CO )(CO Mn CO ± Mn >35 ± 12 1 Mn(CO) ± Mn(CO) ± 11 1 (CO) 5 Mn Re(CO) ± 11 1 )Mn(CO PhMe 59.4 ± (CO) 5 Tc Tc(CO) ± (CO) 5 Re Re(CO) ± (CO) 5 Re 13 1 (CO) 5 Re 220 ± 8 1 (10.8) Group 8 (CO) 4 Fe Fe(CO) (CO) 4 Fe(H) x 59.4 ± )(CO Fe 39 1 Fe(CO (N 2 ) N ± Fe( )(CO) 4 CO 88 ± Fe(CO (PMe 3 ) CO >125 1 Fe(CO (PPh 3 ) CO <177.8 ± 5 1 Fe N 31.4 ± Fe 364 ± 29 1 Fe 135 ± 29 1 Fe( )(CO 89.1 ± 8 1 Fe Fe 79 1 Fe(CO) 5 Ni(CO) Fe(CO) 5 (η 3 - ) Fe( )(CO ~ (C ) )Ru 72 1 (PMe 3 )Ru H (CO )Ru Cl )(PMe 3 Ru Cl <138 1 )(PMe 3 Ru OH (CO) 4 Ru CO 115 ± )(PMe 3 Ru Os(H)(CO) (CO) 4 Os CO 133 ± Os( )(CO) 4 CO 99.5 ± (10.9) Group 9 (CO) 4 Co Co(CO) 4 83 ± 29 1 (CO) 4 Co Mn(CO) 5 96 ± 12 1 (CO) 4 Co Re(CO) ± 15 1 Co(CO) Co(CO )(PPh 3 ) 72 1 (CO HCo CO ~54 1 )Co(CO) CO ± Co 331 ± 38 1 Co 178 ± 8 1 cobalamin cobinamide i Co C bonds in B ± Cl(CO Rh Rh(CO Cl HRh(m-xylyl)Rh 55.6 ± (PiPr 3 (Cl)Rh (PiPr 3 (Cl)Rh N (PiPr 3 (Cl)Rh C HRh(m-xylyl)Rh OH ± Ir(Cl)(CO)(PMe Ir(H) )(PMe 3 ) H ± 21 1 Ir(Cl)(H)(CO)(PEt Ir(Cl)(H)(CO)(PPh (Cl)(CO)(PPh 3 Ir (Cl)(CO)(PPh 3 Ir CO Ir(H) )(PMe 3 ) (10.10) Group 10 Ni O ~29 1 Ni(CO N 2 ~42 1 K11100_S09.indb 79 2/23/10 5:29:20 PM

16 9-80 Bond Dissociation Energies Ni(CO CO ± Ni 208 ± 8 1 Ni 193 ± 25 1 Ni ± Ni propyne 155 ± 21 1 Ni 2-butyne 121 ± 21 1 Pd O13 1 trans-pt(pph 3 (Cl) 07 ± 37 1 [Ph 2 P ] 2 MePt H [Ph 2 P ] 2 MePt OH [Ph 2 P ] 2 MePt S0.0 1 Pt )( 163 ± 21 1 cis-pt(pet 3 ( ) 269 ± 13 1 (10.11) Group 11 Cu OH >406 1 Cu C5 ± 5 1 Cu 223 ± 5 1 Cu N 47 ± 15 1 Cu(N ) N 83.7 ± Cu 16.4 ± Cu( ) 27.0 ± Ag ± Ag N 8 ± 13 1 Ag(N ) N 62.8 ± Au OH >262 1 Au N 76 ± 6 1 Au Au (10.12) Group 12 Zn 70 ± 10 1 Zn( ) ± Zn 92.0 ± Zn( ) ± Cd 63.6 ± Cd( ) ± Hg 22.6 ± Hg( ) ± ClHg ± BrHg 270 ± 38 1 IHg ± (10.13) Group 13 B B B N ± ( B N 57.7 ± F 3 B N( 130 ± Cl 3 B N( F 2 B Al O47 ± 13 1 Al >54 1 Cl 3 Al N( ± ( Al N( ( Al O( 92 1 ( Ga O( 50.6 ± Cl 3 Ga-S( In In( ) In( ( In N( 83.3 ± Tl O30 ± 30 1 References 1. Luo, Y. R. Comprehensive Handbook of Chemical Bond Energies, CRC Press, Boca Raton, FL, Shuman, N. S., Ochieng, M. A., Sztáray, B., and Baer, T., J. Phys. Chem. A 112, 5647, Seetula, J. A., and Eskola, A. J., Chem. Phys. 351, 141, Golden, D. M., Int. J. Chem. Kinet. 41, 573, Shuman, N. S., Spencer, A. P., and Baer, T., J. Phys. Chem. A 113, 9458, TABLE 4. Enthalpies of Formation of Free Radicals and Other Transient Species References: Yu-Ran Luo, Comprehensive Handbook of Chemical Bond Energies, CRC Press, Radical f Η ο /kj 298 mol 1 Ref. (1) Carbon-Centered Species C95.8 ± (triplet91.2 ± (singlet) ± 1.6 1, methyl ± H, acetenyl, CH C ± 2.1 1, vinylidene =C ± , vinyl, =C 99.6 ± 3.3 1, ethyl, C ± 1.3 1, propargyl, CH CC , C C 515 ± 13 1, =C=CH CH CC , cyclopro-2-en-1-yl ± , allyl, =CHC ± 3.0 1, CH=C 67 ± 6 1, C = , cyclopropyl ± Radical f Η ο /kj 298 mol 1 Ref. n-, n-propyl, C 100 ± 2 1 i-, i-propyl, C H 88 ± 3 1 n-, CH CCH=C i-, =C C C99.2 1, C CC , CH CC H , CH=CHCH , =CHC , CH=CHC 146 ± 8 1, =CH C , =C( )C , =CHC H , cyclopropylmethyl ± 6.7 1, cyclobutyl ± n-, n-butyl, C 77.8 ± i-, i-butyl, ( CHC 70 ± 4 1 s-, s-butyl, C H 67.8 ± t-, t-butyl, ( C 48 ± 3 1 K11100_S09.indb 80 2/23/10 5:29:22 PM

17 Bond Dissociation Energies 9-81 Radical f Η ο /kj 298 mol 1 Ref., CH C-C CC , (CH C C , =CHC CC , =CH-C H-C , cyclopenta-1,3-dien-5-yl ± 7.3 1, C CC H ± 9.2 1, CH CC H ± 8.4 1, CH CC ( ± 9.2 1, =CHCH=CHC ± , ( =CH C 08.0 ± 4.2 1, CH=C=CHC , spiropentyl ± 4.2 1, cyclopent-1-en-3-yl ± 4.2 1, cyclopentyl ± 4.2 1, =CHC H ± 8.4 1, CH=CHC H( ) 92 1, CH=C( )C , =CHC ( 87.0 ± 8.4 1, =C( )C H( ) , =C(C ) , =CH( C n, C , ( C 7.0 1, (n )( )C 0.2 1, ( C 36.4 ± 8.4 1, ( )( C 29 1, phenyl ± 3.3 1, cyclohexa-1,3-dien-5-yl , cyclohexa-1,4-dien-3-yl ± 3.9 5, C CC ( ± 9.2 1, ( =CH C ( ) , cyclohexa-1-en-3-yl , =CH( C , =CHC H( , =C( )C ( 37.7 ± 6.3 1, ( C=C( )C 39.7 ± 6.3 1, ( C=CHC H( ) , (Z)- CH=CHC ( , cyclohexyl 75.3 ± n H 13, C H 13, (n )( )C H 13, 2-methyl-2-pentyl 3.3 ± H 13, 3-methyl-3-pentyl H 13, 2,3-dimethyl-2-butyl 3.1 ± 10 1, (CH C C , benzyl, C ± 1.7 1, quadricyclolan-5-yl ± 5.4 1, quadricyclolan-4-yl ± 5.4 1, norborna-2,5-dien-7-yl ± 7.9 1, cyclohepta-1,3,5-trien-7-yl ± , =CH(CH=CH CC Radical f Η ο /kj 298 mol 1 Ref., ( =CH C , norborn-1-yl ± , cycloheptenyl H 13, cycloheptyl 50.6 ± H 13, cyclo-[c ( )( ) 5 ] H 13, cyclo-[c ( )( ) 4 ] H 15, (n )( )CH H 15, ( CHCHC ( 21.8 ± 5.2 1, cubyl ± , C = , CH=CH , C H( ) ± 7.5 1, C ± 7.5 1, p- C , m- C , o- C , 1-vinyl-cyclohexa-2,4-dienyl ± , 2-vinyl-cyclohexa-2,4-dienyl ± , 3-vinyl-cyclohexa-2,4-dienyl ± , 6-vinyl-cyclohexa-2,4-dienyl ± H 13, =CHCH=CHC H( H 13, =CHC H( CH= H 13, bicyclooct-1-yl H 15, =CHC H( ) H 15, (E)- CH=C ( ) H 15, (Z)-( C CH=CHCH( H 15, cyclooctanyl H 15, cyclo-[c ( )( ) 5 ] C 9, indenyl C 9, indanyl ± C 9, 2,6-dimethylbenzyl C 9, 3,6-dimethylbenzyl C 9, 3,5-dimethylbenzyl C 9, C ( ± C 9, o ± C 9 H 17, cyclononanyl C 10, naphth-1-yl ± C 10, naphth-2-yl ± C 10, tetralin-1-yl ± C 10 H 13, 1-phenyl-but-4-yl C 10 H 13, ( )( )C H C 10 H 13, ( )( )C H C 10 H 13, ( C H C 10 H 15, 1-adamantyl C 10 H 15, 2-adamantyl C 10 H 19, cyclodecanyl C 11, 1-naphthylmethyl C 11 1, cycloundecanyl C 12 3, cyclododecanyl C 13, 9-fluorenyl C 13, ( C 02.1 ± K11100_S09.indb 81 2/23/10 5:29:24 PM