Ref. p. 329] 3 Radicals in metal complexes Substance Generation / Matrix or Solvent / Method / T [K] 285 g-Factor / a-Value [mT] Ref. / add. Ref. 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [C9H5NO2Tl] • O Tl chemical reduction • THF / HMPTA (3:1) ESR / ENDOR / 295 N O 91Boc 203,205 Tl: 3.130 H(1): 0.440 H(2): 0.170 H(3): 0.130 electrochemistry, HMO calculations [C10H12InN4] •2+ •2+ In N N CH3 chemical reaction 115 In: 0.59 2.00434 85Ste 203,205 • O pyridine O ESR / 298 Tl(CH3)2 O [C10H22B2N2] •− •− Me3B N 94Mat ESR / RT [C10H12O3Tl] • H3C 2.0000 acetonitrile N H3C N reduction of ligand with indium metal Tl: 1.995 H(3): 0.190 H(5): 0.275 H(6): 0.085 chemical reduction 2.0035 THF 11 92Lic B: 0.237 N: 0.803 H(2): 0.254 H(18 H): 0.016 14 N BMe3 ESR / 300 ENDOR / 305 electrochemistry, MO calculations [C12H19NO2Tl] • H2N • O Tl(CH2CH3)2 O [C11H12O4Tl] • HOOC 2.00397 pyridine 203,205 ESR / 298 • O Tl(CH3)2 pyridine ESR / 298 85Ste Tl: 1.810 H(3): 0.050 H(5): 0.370 H(6): 0.100 H(7): 0.300 chemical reaction O Landolt-Börnstein New S eries II/ 26A2 chemical reaction 85Ste 203,205 Tl: 2.08 H(3): 0.043 H(5): 0.290 H(6): 0.121 H(7): 0.230 H(8): 0.121 286 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [Ref. p. 329 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C12H17O2Tl] • chemical reaction 2.00349 85Sch pyridine 203,205 • O Tl(CH3)2 H2N ESR / RT O [C12H17NO2Tl] • chemical reaction • O H3C Tl(CH3)2 N [C13H18O2Tl] • • O Tl(CH3)2 H3C pyridine ESR / 223 O • 85Sch 203,205 Tl: 2.038 H(5,8): 0.076 H(1, ax): 0.688 H(1, eq): 0.341 H(4, ax): 0.787 H(4, eq): 0.359 pyridine 2.00353 ESR / RT 203,205 Tl: 2.228 H(5,8): 0.076 chemical reaction 2.00348 pyridine 203,205 ESR / RT O [C14H20InO2] Tl: 2.23 H(5,8): 0.060 H(1, ax): 0.690 H(1, eq): 0.415 H(4, ax): 0.670 H(4, eq): 0.445 Tl: 2.21 H(5,8): 0.0615 H(1, ax): 0.733 H(1, eq): 0.3805 H(4, ax): 0.724 H(4, eq): 0.4105 chemical reaction • toluene / 4-methylpyridine tBu ESR / 298 O 85Sch 89Ann 115 In: 0.983 H(4): 0.322 In tBu toluene / pyridine O ESR / 298 [C14H20Br2InO2] • • tBu O InBr2 tBu O 115 In: 1.04 H(4): 0.340 chemical reaction 2.0039 dichloromethane / 4-methylpyridine 115 90Ann In: 0.540 H(4): 0.320 ESR / 213 Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes Substance Generation / Matrix or Solvent / Method / T [K] [C14H20I2InO2] • • toluene / 4-methylpyridine O ESR / 298 InI2 O THF / 4-methylpyridine ESR / 298 [C14H21NO4Tl] • H3C HOOC • O TlEt2 NH2 O [C18H14O2Tl] • 115 In: 0.644 H(4): 0.320 115 In: 0.510 H(4): 0.350 chemical reaction 2.00388 pyridine 203,205 ESR / 298 TlPh2 pyridine Ref. / add. Ref. 89Ann 85Ste Tl: 1.84 H(3): 0.059 H(5): 0.345 H(6): 0.097 H(7): 0.290 H(7): 0.205 chemical reaction • O g-Factor / a-Value [mT] chemical reaction tBu tBu 287 88Ste2 203,205 Tl: 1.172 ENDOR / 295 O THF 203,205 Tl: 1.400 ENDOR / 295 toluene 203,205 Tl: 1.400 ENDOR / 295 [C16H22AlN2] • • chemical reaction 2.0028 n-pentane 27 94Has Al: 0.457 N: 0.314 H(4): 0.285 H(5): 0.285 14 N ESR / 295 AliPr2 N electrochemistry, UV-VIS and mass spectroscopy [C16H22GaN2] • • chemical reaction 2.0031 n-pentane 69 Ga: 1.332 Ga: 1.692 14 N: 0.350 H(4): 0.350 H(5): 0.223 H(6): 0.056 71 N ESR / 295 GaiPr2 N electrochemistry, UV-VIS and mass spectroscopy Landolt-Börnstein New S eries II/ 26A2 94Has 288 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [Ref. p. 329 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C16H34B2N2] •− chemical reduction 2.0035 92Lic THF 11 •− B: 0.259 B: 0.087 14 N: 0.802 H(2): 0.261 H: 0.008 10 N BEt 3 Et3B N ESR / 300 ENDOR / 220 electrochemistry, MO calculations [C16H36Al2Si2] •− Me3Al AlMe3 C C C C Me3Si SiMe3 •− THF ESR / 300 chemical reaction Al: 0.301 Si: 0.55 2.00405 pyridine O ESR / 298 TlPh2 O [C19H16O2Tl] • Tl: 1.07 H(3): 0.128 H(5): 0.323 H(6): 0.075 chemical reaction • CH3 85Ste 203,205 • O 27 29 [C19H14O4Tl] • HO 88Kai chemical reaction pyridine O 88Ste2 203,205 Tl: 1.295 ENDOR / 295 TlPh2 O [C19H20NO2Tl] • • H3C N chemical reaction 2.00358 pyridine 203,205 ESR / 298 Tl: 2.40 H(5): 0.360 H(6): 0.110 H(7): 0.840 H(7): 0.165 chemical reaction 2.0031 THF D = 15.7 mT O Tl(CH3)2 85Ste O [C20H16AlFN4] 2• 2• 91Row ESR / 77 N N Al N F adamantane 2.0016 ESR / 77 D = 17.3 mT N UV-VIS, IR and 19F-NMR spectroscopy Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 289 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C20H16O3Tl] • chemical reaction 2.00426 85Ste pyridine 203,205 • O O H3C TlPh2 ESR / 298 Tl: 0.915 H(3): 0.178 H(5): 0.283 H(6): 0.075 chemical reaction 2.00362 pyridine 203,205 O [C20H16O4Tl] • • O HOOC TlPh2 O [C20H16O4Tl] • • O H3C O O TlPh2 ESR / 298 Tl: 1.12 H(3): 0.045 H(5): 0.370 H(6): 0.090 H(7): 0.320 chemical reaction 2.00375 pyridine 203,205 ESR / 298 Tl: 1.14 H(3): 0.06 H(5): 0.360 H(6): 0.10 H(7): 0.295 chemical reaction 2.00370 pyridine 203,205 O [C20H19NO2Tl] • H2N • O TlPh2 ESR / 298 O [C20H19NO3Tl] • • OH O H2N TlPh2 [C20H24BrInN2O2] •+ or dimer Br O CH3 N CH3 In O Landolt-Börnstein New S eries II/ 26A2 N CH 3 CH3 •+ 2.00366 pyridine 203,205 ESR / 298 Tl: 1.16 H(3): 0.05 H(5): 0.370 H(6): 0.09 H(7): 0.310 chemical reaction 2.0039 toluene 115 ESR / 298 85Ste 85Ste Tl: 1.155 H(3): 0.040 H(5): 0.372 H(6): 0.095 H(7): 0.305 chemical reaction O 85Ste In: 0.473 H(1): 0.23 H(2): 0.23 H(3): 0.21 H(4): 0.15 85Ste 90Ann 290 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) Substance [C20H24ClInN2O2] •+ or dimer CH3 N CH3 Cl O •+ Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. chemical reaction 2.0039 90Ann toluene 115 ESR / 298 In: 0.485 H(1): 0.23 H(2): 0.23 H(3): 0.21 H(4): 0.15 chemical reaction 2.0039 toluene 115 In O [Ref. p. 329 N CH 3 CH3 [C20H24IInN2O2] •+ or dimer CH3 N CH3 I O •+ ESR / 298 In: 0.462 H(1): 0.23 H(2): 0.23 H(3): 0.21 H(4): 0.15 chemical reduction near 2.00 97Gri chemical reaction 2.0039 90Ann toluene / dichloromethane 115 In O 90Ann N CH 3 CH3 [C20H28B2O2] •− (Me s)(H 3 CO)B B(OCH 3)(Mes ) •− THF ESR / 298 crystal structure [C20H36Br2InN2O2] • tBu Br O CH3 N CH3 • In: 0.740 ESR / 298 In tBu O Br N CH 3 CH3 [C20H36Cl2InN2O2] • tBu Cl O CH3 N CH3 • chemical reaction 2.0039 toluene / dichloromethane 115 90Ann In: 0.760 ESR / 298 In tBu O Cl N CH 3 CH3 Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 291 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C20H36I2InN2O2] • chemical reaction 2.0039 90Ann toluene / dichloromethane 115 tBu CH3 N CH3 I O • In: 0.710 ESR / 298 In tBu O N CH 3 CH3 I [C20H40AlN4] • • tBu N hexane 27 Al: 0.5 N(2 N): 0.5 H(2 H): 0.5 90Clo chemical reaction 2.0024 91Kai1 hexane 69,71 Ga: 1.8 other hfs 89Clo chemical reaction 2.00372 85Ste pyridine 203,205 2 crystal structure • tBu N ESR / 298 Ga 2 N tBu crystal structure [C21H16O4Tl] • HOOC • O TlPh2 ESR / 298 O [C21H19NO3Tl] • H3C 91Kai1 ESR / 298 [C20H40GaN4] • H N 2.0018 14 Al N tBu chemical reaction chemical reaction • O O TlPh2 [C22H21O2NTl] • • O TlPh2 Landolt-Börnstein New S eries II/ 26A2 O 85Ste 203,205 pyridine ESR / 298 O H2N Tl: 1.125 H(3): 0.035 H(5): 0.300 H(6): 0.113 H(7): 0.231 H(8): 0.124 Tl: 0.915 H(3): 0.160 H(5): 0.285 H(6): 0.065 chemical reaction 2.00349 pyridin 203,205 ESR / RT Tl: 1.17 H(5,8): 0.055 H(1, ax): 0.722 H(1, eq): 0.417 H(4, ax): 0.702 H(4, eq): 0.459 85Sch 292 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [Ref. p. 329 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C21H21NO3Tl] • chemical reaction 2.00361 85Ste pyridine 203,205 H3C • OH H N O ESR / 298 Tl: 1.16 H(3): 0.05 H(5): 0.365 H(6): 0.09 H(7): 0.305 chemical reaction 2.00346 pyridine 203,205 TlPh2 O [C22H20O2Tl] • • O TlPh2 O [C22H21NO3Tl] • • H N H3C chemical reaction 2.00366 pyridine 203,205 ESR / 298 Tl: 1.135 H(3): 0.045 H(5): 0.370 H(6): 0.100 H(7): 0.310 chemical reaction 2.00362 pyridine 203,205 O TlPh2 O O [C22H21NO4Tl] • • O H3C ESR / RT Tl: 1.19 H(5,8): 0.055 H(1): 0.57 H(4): 0.57 O O NH2 ESR / 298 TlPh2 O [C22H38B2N2] •− •− Et3B N N BEt 3 85Sch 85Ste 85Ste Tl: 1.19 H(3): 0.05 H(5): 0.365 H(6): 0.10 H(7): 0.295 H(7): 0.245 chemical reduction 2.0032 THF 11 92Lic B: 0.138 B: 0.046 14 N: 0.420 H(2): 0.078 H(3): 0.203 H: 0.004 10 ESR / 300 ENDOR / 200 electrochemistry, MO calculations [C22H48Al2Si2] •− Et3Al AlEt3 C C C C Me3Si SiMe3 chemical reaction •− THF 88Kai 27 Al: 0.309 Si: 0.55 29 ESR / 300 Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 293 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C23H22O2Tl] • chemical reaction 2.00345 85Sch pyridine 203,205 • O TlPh2 H3C ESR / RT O [C23H23NO3Tl] • H2N • O chemical reaction 2.00378 pyridine 203,205 ESR / ENDOR / 298 O H3C TlPh2 O [C23H23NO3Tl] • chemical reaction Et pyridine O N Et ESR / 298 TlPh2 Tl: 1.033 H(3): 0.052 H(5): 0.360 H(6): 0.093 H(7): 0.123 H(8): 0.0125 2.00383 85Ste Tl: 1.15 H(3): 0.097 H(5): 0.335 H(6): 0.085 O [C23H25NO3Tl] • • OH H N H3C 85Ste 203,205 • O Tl: 1.187 H(5,8): 0.0555 H(1, ax): 0.755 H(1, eq): 0.3815 H(4, ax): 0.750 H(4, eq): 0.4165 O TlPh2 CH3 chemical reaction 2.00361 pyridine 203,205 ESR / 298 O [C24H16TlN2O2] • • N O 85Ste Tl: 1.165 H(3): 0.053 H(5): 0.365 H(6): 0.091 H(7): 0.311 14 N: 0.0155 electrochemically generated 2.0041 THF 203,205 92Boc1 Tl: 0.25 ESR / 295 TlPh 2 O N HMO calculations [C24H24O2Tl] • • O H3C H3C Landolt-Börnstein New S eries II/ 26A2 TlPh2 O chemical reaction 2.00348 pyridine 203,205 ESR / RT Tl: 1.185 H(5,8): 0.056 H(1): 0.550 H(4): 0.580 85Sch 294 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [Ref. p. 329 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C24H24O5Tl] • chemical reaction 2.00359 85Ste pyridine / triethanolamine 203,205 • OH O HOOC Tl(pXylyl)2 ESR / 298 Tl: 1.90 H(3): 0.042 H(5): 0.380 H(6): 0.084 H(7): 0.362 chemical reaction 2.0039 toluene 115 O [C24H30BrInN2O2] • • tBu O ESR / 298 In(Py)2Br tBu In: 1.014 H(4): 0.319 O [C24H30BrInN2O2] • 2+ • 2+ tBu O tBu chemical reaction 2.0039 toluene / dichloromethane 115 ESR / 298 In(Py)2Br 90Ann In: 0.633 H(4): 0.353 O [C24H30Br2InN2O2] • • tBu O In(Py)2Br2 tBu chemical reaction 2.0039 THF 115 ESR / 298 In: 0.513 H(4): 0.385 H(5): 0.034 chemical reaction 2.0039 toluene 115 90Ann O [C24H30ClInN2O2] • • tBu O ESR / 298 In(Py)2Cl tBu 90Ann In: 1.072 H(4): 0.331 O [C24H30ClInN2O2] • 2+ • 2+ tBu O tBu chemical reaction 2.0039 toluene / dichloromethane 115 ESR / 298 In(Py)2Cl 90Ann In: 0.651 H(4): 0.348 O [C24H30Cl2InN2O2] • • tBu O In(Py)2Cl2 tBu 90Ann chemical reaction 2.0039 THF 115 ESR / 298 90Ann In: 0.638 H(4): 0.331 H(5): 0.031 O Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 295 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C24H46AlN2Si4] • chemical reaction 2.0030 94Has n-pentane 27 • N ESR / 295 Al[CH(SiMe3)2]2 N Al: 0.400 N: 0.299 H(3): 0.027 H(4): 0.304 H(5): 0.269 H(6): 0.027 electrochemistry, UV-VIS and mass spectroscopy [C25H26O4Tl] • chemical reaction • O pyridine O HO ESR / 298 Tl(Mes)2 O [C25H29NO2Tl] • • O H2N Tl(Mes)2 [C25H29NO3Tl] • H3C • OH Landolt-Börnstein New S eries II/ 26A2 2.00330 pyridine 203,205 O Tl(pXylyl)2 pyridine ESR / ENDOR / 298 85Ste Tl: 2.190 H(3): 0.032 H(5): 0.375 H(6): 0.075 H(7): 0.450 chemical reaction O 85Ste Tl: 2.25 H(3): 0.120 H(5): 0.325 H(6): 0.066 chemical reaction ESR / 298 O H N 2.00377 203,205 85Ste 203,205 Tl: 1.78 H(3): 0.048 H(5): 0.364 H(6): 0.091 H(7): 0.317 H(8): 0.007 296 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [Ref. p. 329 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C25H38N3O5Ga] •+ electrochemically generated 2.006 01Kim •+ O O acetonitrile ESR / 50 N O O Ga N N O tBu electrochemistry, UV-VIS spectroscopy tBu [C26H18O2Tl] • • O chemical reaction 2.0034 pyridine 203,205 ESR / ENDOR / 293 Tl: 0.740 H(1,8): 0.159 H(2,7): 0.039 H(3,6): 0.171 H(4,5): 0.037 chemical reaction 2.0036 THF 115 TlPh2 O [C26H22I2InN2O2] • CH3 • ESR / 300 88Ste2 98Bro2 In: 0.26 H: 0.225 H: 0.135 N O InI2 O N CH3 [C26H28O4Tl] • HOOC • O Tl(Mes)2 O chemical reaction 2.00328 pyridine 203,205 ESR / 298 85Ste Tl: 2.19 H(3): 0.045 H(5): 0.375 H(6): 0.075 H(7): 0.330 Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 297 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C26H28O5Tl] • chemical reaction 2.00315 85Ste pyridine / triethanolamine 203,205 • OH O HOOC ESR / 298 Tl(Mes)2 O • [C26H28I2InN2O2] chemical reaction • tBu Tl: 2.30 H(3): 0.037 H(5): 0.365 H(6): 0.07 H(7): 0.365 I ESR / 298 N O toluene 89Ann 115 In: 0.745 H(4): 0.350 In tBu N O I [C26H28O3Tl] • chemical reaction • O O H3C Tl(Mes)2 pyridine ESR / 298 O [C26H30O2Tl] • tBu 2.00397 Tl: 2.11 H(3): 0.159 H(5): 0.293 H(6): 0.066 chemical reaction • O TlPh2 O tBu 85Ste 203,205 pyridine 88Ste2 203,205 Tl: 1.455 ENDOR / 295 THF 203,205 Tl: 1.645 ENDOR / 295 toluene 203,205 Tl: 2.120 ENDOR / 295 [C26H30O2Tl] • chemical reaction • tBu O TlPh2 O pyridine 88Ste2 203,205 Tl: 2.000 ENDOR / 295 THF 203,205 Tl: 2.120 tBu ENDOR / 295 toluene ENDOR / 295 Landolt-Börnstein New S eries II/ 26A2 203,205 Tl: 2.840 298 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [Ref. p. 329 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C26H31NO2Tl] • chemical reaction 2.00328 85Ste pyridine 203,205 H2N • O Tl(Mes)2 O [C26H31NO3Tl] • H2N • O ESR / 298 Tl: 2.150 H(3): 0.030 H(5): 0.380 H(6): 0.085 H(7): 0.310 ethanol 2.00329 ESR / 298 203,205 Tl: 2.180 H(3): 0.030 H(5): 0.375 H(6): 0.085 H(7): 0.305 pyridine / water 2.00329 ESR / 298 203,205 Tl: 1.930 H(3): 0.030 H(5): 0.370 H(6): 0.080 H(7): 0.320 chemical reaction 2.00365 2-methyl-THF 203,205 ESR / 298 Tl: 1.602 Tl: 1.419 H(3): 0.064 H(6): 0.096 H(7): 0.255 chemical reaction 2.00263 pyridine 203,205 203,205 Tl(Mes)2 O OH [C26H31NO3Tl] • • O H2N Tl(Mes)2 HO O [C26H31NO3Tl] • • OH H2N O Tl(Mes)2 O 85Ste ESR / 298 Tl: 1.488 H(3): 0.060 H(5): 0.060 H(7): 0.393 chemical reaction 2.00396 pyridine 203,205 ESR / 298 85Ste 85Ste Tl: 2.16 H(3): 0.045 H(5): 0.370 H(6): 0.08 H(7): 0.330 Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 299 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C26H34BrInN2O2] • chemical reaction 2.0039 90Ann toluene 115 • CH3 ESR / 298 tBu In: 0.990 H(4): 0.320 N O In tBu Br O N CH3 [C26H34BrInN2O2] •2+ • 2+ CH3 tBu chemical reaction 2.0039 toluene / dichloromethane 115 ESR / 298 In: 0.547 H(4): 0.320 H(5): 0.037 chemical reaction 2.0039 benzene 115 90Ann N O In tBu Br O N CH3 [C26H34Br2InN2O2] • CH3 • ESR / 298 tBu N toluene InBr2 ESR / 298 O tBu O N CH3 Landolt-Börnstein New S eries II/ 26A2 crystal structure In: 0.577 H(4): 0.361 115 In: 0.547 H(4): 0.320 H(5): 0.037 90Ann 300 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [Ref. p. 329 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C26H34Cl2InN2O2] • chemical reaction 2.0039 90Ann benzene 115 • CH3 ESR / 298 tBu In: 0.611 H(4): 0.353 N O InCl2 tBu O N CH3 [C26H34I2InN2O2] • • CH3 chemical reaction 2.00391 toluene 115 ESR / 300 tBu 96Bro2 In: 0.486 H(4): 0.342 H(5): 0.036 N O InI2 tBu O N CH3 crystal structure [C27H30O4Tl] • HOOC • O Tl(Mes)2 O [C27H31NO2Tl] • • Tl(Mes)2 O 2.003295 2-methyl-THF 203,205 ESR / 298 dichloromethane 85Ste Tl: 2.28 H(3): 0.03 H(5): 0.373 H(6): 0.083 H(7): 0.340 chemical reaction O HN chemical reaction 85Sch ESR / 172 H(1, ax): 0.73 H(1, eq): 0.4 H(4, ax): 0.85 H(4, eq): 0.34 dichloromethane 2.00296 ESR / RT 203,205 85Sch Tl: 2.34 H(5,8): 0.044 H(1): 0.552 H(4): 0.584 (continued) Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 301 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] [C27H31NO2Tl] • (continued) pyridine 2.00308 ESR / RT 203,205 [C27H31NO3Tl] • H3C H N chemical reaction ESR / 298 chemical reaction 2.00342 pyridine 203,205 Tl(Mes)2 O • • O HOOC Tl(Mes)2 NH2 ESR / 298 O [C27H31NO5Tl] • • OH O HOOC Tl(Mes)2 NH2 H3C • OH 2.00335 pyridine / water 203,205 ESR / 298 Tl: 2.02 H(3): 0.040 H(5): 0.360 H(6): 0.080 H(7): 0.470 chemical reaction 2.00335 pyridine 203,205 O Tl(Mes)2 ESR / 298 Tl: 2.18 H(3): 0.04 H(5): 0.370 H(6): 0.075 H(7): 0.323 chemical reaction 2.00367 pyridine 203,205 O [C27H37NO2Tl] • • H3C N ESR / 298 O Tl(2-iC5H11)2 O Landolt-Börnstein New S eries II/ 26A2 85Ste 85Ste Tl: 2.10 H(3): 0.039 H(5): 0.365 H(6): 0.080 H: 0.091 H: 0.562 chemical reaction O [C27H33NO3Tl] • H N 2.00396 Tl: 2.14 H(3): 0.160 H(5): 0.290 H(6): 0.070 H(2 H): 0.03 pyridine O [C27H31NO4Tl] Tl: 2.172 H(5,8): 0.046 H(1): 0.549 H(4): 0.576 203,205 • O Ref. / add. Ref. Tl: 2.70 H(5): 0.365 H(6): 0.110 H(7): 0.855 H(7): 0.169 85Ste 85Ste 85Ste 302 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [Ref. p. 329 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C28H18O6Tl] • chemical reaction 2.0033 88Ste2 pyridine 203,205 • O O O O ESR / ENDOR / 293 Tl: 0.717 H(1,8): 0.219 H(2,7): 0.056 H(CH2): 0.042 chemical reaction 2.0032 pyridine 203,205 TlPh2 O O [C28H18O6Tl] • • O O ESR / ENDOR / 293 O TlPh2 88Ste2 Tl: 0.825 H(1,8): 0.146 H(4,5): 0.023 H(CH2): 0.007 O O O [C28H22O2Tl] • • CH3 chemical reaction 2.0034 pyridine 203,205 ESR / ENDOR / 293 Tl: 0.782 H(1,8): 0.166 H(2,7): 0.038 H(3,6): 0.166 H(4,5): 0.038 chemical reaction 2.0033 pyridine 203,205 O TlPh2 O 88Ste2 CH3 [C28H22O2Tl] • • H3C O ESR / ENDOR / 293 Tl: 0.805 H(1,8): 0.160 H(2,7): 0.040 H(3,6): 0.188 H(4,5): 0.036 chemical reaction 2.0035 pyridine 203,205 TlPh2 O 88Ste2 H3C [C28H22O2Tl] • • H3C H3C O ESR / ENDOR / 293 TlPh2 O 88Ste2 Tl: 0.515 H(1,8): 0.177 H(2,7): 0.047 H(3,6): 0.177 H(4,5): 0.038 Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 303 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C28H32O2Tl] • chemical reaction 2.00305 85Sch pyridine 203,205 • O Tl(Mes)2 ESR / RT O ethylchloride / methylpentane [C28H33NO2Tl] • • O Tl(Mes)2 HN O ESR / 123 H(1, ax): 0.87 H(1, eq): 0.36 H(4, ax): 0.87 H(4, eq): 0.36 dichloromethane 2.00292 ESR / RT 203,205 Tl: 2.295 H(5,8): 0.037 H(1): 0.595 H(4): 0.595 chemical reaction 2.00327 ether 203,205 ESR / 223 Tl: 2.36 H(1, ax): 0.612 H(4, ax): 0.75 H(4, eq): 0.412 chemical reaction 2.00297 dichloromethane 203,205 CH3 [C28H33NO2Tl] • • O Tl(Mes)2 H2N ESR / RT O [C28H33NO3Tl] • H N H3C O (continued) Landolt-Börnstein New S eries II/ 26A2 • Tl(Mes)2 2.00311 ESR / RT 203,205 Tl: 2.15 H(5,8): 0.043 H(1, ax): 0.726 H(1, eq): 0.431 H(4, ax): 0.708 H(4, eq): 0.470 chemical reaction 2.00336 pyridine 203,205 ESR / 298 85Sch 85Sch Tl: 2.33 H(5,8): 0.043 H(1, ax): 0.725 H(1, eq): 0.430 H(4, ax): 0.725 H(4, eq): 0.465 pyridine O O Tl: 2.15 H(5,8): 0.044 H(1): 0.583 H(4): 0.583 Tl: 2.140 H(3): 0.035 H(5): 0.370 H(6): 0.085 H(7): 0.315 85Ste 304 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) Substance Generation / Matrix or Solvent / Method / T [K] [C28H33NO3Tl] • (continued) ethanol g-Factor / a-Value [mT] [Ref. p. 329 Ref. / add. Ref. 2.00329 203,205 [C28H33NO4Tl] • • O H3C O O chemical reaction 2.00333 pyridine 203,205 O [C28H39NO2Tl] • tBu Tl: 2.180 H(3): 0.030 H(5): 0.375 H(6): 0.85 H(7): 0.305 ESR / 298 Tl(Mes)2 NH2 ESR / 298 • tBu ESR / 298 chemical reaction 2.0032 THF 115 tBu [C28H40I4In2O4]2 • 2• I tBu O I O In O In ESR / 300 O I tBu tBu D: 10.3 (100 K) tBu 2• I I tBu [C28H40O5Tl] • tBu H3C O Tl(thf)(CH3)2 O O O In: 0.893/0.850 H(4): 0.365 O In O I O In O 98Bro2 tBu tBu I 203,205 Tl: 4.70 N: 0.67 H(3): 0.28 H(7): 0.35 H(9): 0.24 toluene O tBu 89Kar 14 tBu I Tl: 2.20 H(3): 0.04 H(5): 0.365 H(6): 0.082 H(7): 0.300 H(7): 0.250 chemical reduction O Tl N 85Ste CH3 • chemical reaction 2.0039 THF 203,205 ESR / RT 98Aba Tl: 2.8 H(1 H): 0.31 H(6 H): 0.06 tBu Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 305 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C28H76Al2Si8] •− chemical reaction 2.0035 93Plu THF 27 •− (Me3Si)2HC CH(SiMe3)2 Al Al (Me3Si)2HC CH(SiMe3)2 Al: 1.19 Si: 0.4 29 ESR / 333 chemical reaction 2.0025 93Uhl 27 diethylether Al: 1.11 Si: 0.435 29 ESR / 295 and 110 UV-VIS and IR spectroscopy [C28H76Ga2Si8] •− chemical reaction •− CH(SiMe3)2 (Me3Si)2HC GaGa CH(SiMe3)2 (Me3Si)2HC 2.0037 95Uhl 69 1,2-dimethoxyethane ESR / 310 Ga: 5.74 71 Ga: 7.28 29 Si: 0.53 crystal structure, UV-VIS and IR spectroscopy [C29H24O2Tl] • • CH3 O H3C chemical reaction 2.0033 pyridine 203,205 ESR / ENDOR / 293 Tl: 1.00 H: 0.181 H: 0.166 H: 0.043 H: 0.027 chemical reaction 2.00357 pyridine 203,205 TlPh2 O 88Ste2 CH3 [C29H25NO2Tl] • • H3C N ESR / 298 Tl: 1.355 H(5): 0.365 H(6): 0.105 H(7): 0.860 H(7): 0.180 chemical reaction 2.00307 pyridine 203,205 O TlPh2 85Ste O [C29H34O2Tl] • • O Tl(Mes)2 H3C Landolt-Börnstein New S eries II/ 26A2 O ESR / RT Tl: 2.145 H(5,8): 0.045 H(1, ax): 0.765 H(1, eq): 0.390 H(4, ax): 0.759 H(4, eq): 0.427 85Sch 306 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) Substance Generation / Matrix or Solvent / Method / T [K] [C29H35NO3Tl] • chemical reaction • O Et O N Et Tl(Mes)2 • CH3 H3C pyridine ESR / 298 Ref. / add. Ref. 2.00360 85Ste Tl: 2.16 H(3): 0.085 H(5): 0.335 H(6): 0.085 chemical reaction 2.0033 pyridine 203,205 ESR / ENDOR / 293 Tl: 0.740 H(1,8): 0.167 H(2,7): 0.043 H(3,6): 0.197 H(4,5): 0.038 chemical reaction 2.0033 pyridine 203,205 O TlPh2 H3C g-Factor / a-Value [mT] 203,205 O [C30H26O2Tl] • [Ref. p. 329 O 88Ste2 H3C [C30H26O2Tl] • • CH3 H3C ESR / ENDOR / 293 Tl: 0.845 H(1,8): 0.165 H(2,7): 0.038 H(3,6): 0.192 H(4,5): 0.038 chemical reaction 2.0034 pyridine 203,205 O TlPh2 O 88Ste2 H3C CH3 [C30H26O2Tl] • • H3C O H3C H3C ESR / ENDOR / 293 Tl: 0.489 H(1,8): 0.177 H(2,7): 0.050 H(3,6): 0.186 H(4,5): 0.040 chemical reaction 2.0034 pyridine 203,205 TlPh2 O 88Ste2 H3C [C30H26O2Tl] • • CH3 ESR / ENDOR / 293 O H3C H3C TlPh2 O 88Ste2 Tl: 0.560 H(1,8): 0.170 H(2,7): 0.042 H(3,6): 0.179 H(4,5): 0.042 CH3 Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 307 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C30H26O6Tl] • chemical reaction 2.0032 88Ste2 pyridine 203,205 • OCH3 H3CO ESR / ENDOR / 293 Tl: 0.875 H(1,8): 0.145 H(2,7): 0.005 H(3,6): 0.018 H(4,5): 0.018 chemical reaction 2.00313 pyridine 203,205 O TlPh2 O H3CO OCH3 [C30H36O2Tl] • • O Tl(Mes)2 H3C H3C ESR / RT O Tl: 2.12 H(5,8): 0.045 H(1): 0.558 H(4): 0.593 dichloromethane [C31H53GaN3O4] • 2+ N 2+ CH3 ESR / 156 H(1, ax): 0.881 H(1, eq): 0.298 H(4, ax): 0.838 H(4, eq): 0.449 dichloromethane 2.00303 ESR / RT 203,205 Tl: 2.25 H(5,8): 0.036 H(1): 0.560 H(4): 0.600 electrochemically generated 2.004 dichloromethane 69 ESR / 4–70 Ga O N tBu O tBu MeO Landolt-Börnstein New S eries II/ 26A2 85Sch 85Sch 00Mül Ga: 0.258 Ga: 0.215 14 N: 0.214 H(CH2): 0.338 H(benzylic): 0.189 H(benzylic): 0.143 H(CH3): 0.221 71 O tBu H3C N 85Sch d2-deuterated H(CD2): 0.052 electrochemistry, UV-VIS and resonance Raman spectroscopy 308 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) Substance Generation / Matrix or Solvent / Method / T [K] [C32H24O2Tl] • chemical reaction • CH3 pyridine O CH3 ENDOR / 293 TlPh2 O [C32H30O2Tl] • • CH3 H3C O H3C H3C 203,205 Tl: 0.739 H: 0.175 H: 0.143 H: 0.088 H: 0.061 H: 0.027 2.0034 pyridine 203,205 ESR / ENDOR / 293 O Ref. / add. Ref. 88Ste2 chemical reaction TlPh2 H3C g-Factor / a-Value [mT] [Ref. p. 329 88Ste2 Tl: 0.875 H(1,8): 0.193 H(2,7): 0.038 H(3,6): 0.193 H(4,5): 0.038 CH3 [C33H38B2] •− chemical reduction (Mes)PhB B(Mes)2 •− THF 97Gri 11 B (2 B): 1.3 ESR / 298 crystal structure [C34H22O2Tl] • chemical reaction • pyridine O ENDOR / 293 TlPh2 O [C34H33NO4Tl] • chemical reaction • OH HO N Tl(Mes)2 O 203,205 Tl: 0.607 H: 0.077 H: 0.053 H: 0.020 2.00332 85Ste 203,205 pyridine ESR / 298 O 88Ste2 Tl: 2.17 H(3): 0.030 H(5): 0.364 H(6): 0.090 H: 0.387 H: 0.405 Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 309 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C34H34O2Tl] • chemical reaction 2.0032 88Ste2 pyridine 203,205 • CH3 H3C CH3 ESR / ENDOR / 293 Tl: 0.980 H(1,8): 0.182 H(2,7): 0.043 H(3,6): 0.192 H(4,5): 0.042 chemical reaction 2.003 toluene 69,71 O H3C H3C TlPh2 O H3C CH3 CH3 [C34H56GaN2O4] • • tBu H3C CH3 ESR / 210 94Lan Ga: 0.66 H(4 H): 0.188 tBu O N O Ga N O CH3O H3C tBu tBu UV-VIS and IR spectroscopy [C35H37NO2Tl] • chemical reaction • H3C N 85Ste 203,205 ESR / 298 Tl: 2.425 H(5): 0.360 H(6): 0.098 H(7): 0.870 H(7): 0.180 electrochemically generated 2.004 dichloromethane 69 pyridine O Tl(Mes)2 O [C35H45GaN3O4] • 2+ N • 2+ CH3 O Ph H3C N O ESR / 298 Ph O tBu MeO Landolt-Börnstein New S eries II/ 26A2 Ga: 0.258 Ga: 0.215 14 N: 0.214 H(CH2): 0.338 H(benzylic): 0.189 H(benzylic): 0.143 H(CH3): 0.221 71 Ga N 00Mül d2-deuterated H(CD2): 0.052 crystal structure, electrochemistry, UV-VIS and resonance Raman spectroscopy 310 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) Substance Generation / Matrix or Solvent / Method / T [K] [C36H81Ga2Si3] • chemical reaction [Ref. p. 329 g-Factor / a-Value [mT] Ref. / add. Ref. 2.0035 97Wib 69 Ga Ga pentane • Si(tBu)3 Si(tBu)3 ESR / 298 Si(tBu)3 Ga: 5.0 Ga: 6.4 69 Ga: 3.2 71 Ga: 4.1 71 crystal structure [C37H40O5Tl] • • tBu chemical reaction 2.0033 pyridine 203,205 ESR / ENDOR / 293 O tBu CH3O 88Ste2 Tl: 0.632 H(1,8): 0.164 H(3,6): 0.176 TlPh2 O CH3O OCH3 [C38H44InN2O2S2] • chemical reaction • 89Ann 115 toluene In: 0.651 H(4): 0.353 ESR / 298 tBu Me S O N In tBu O N S [C38H44InN2O2Se2] Me • chemical reaction • toluene ESR / 298 O 115 In: 0.606 H(4): 0.325 Me Se tBu 89Ann N In tBu O N Se Me Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 311 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C38H50GaN2O4] • chemical reaction 2.003 93Oza pyridine 71 • tBu ESR / 363 tBu tBu O O Ga: 0.740 H: 0.184 O Ga O tBu N N magnetic susceptibility [C40H48B2N2] •+ •+ 2.0029 92Lic dichloromethane 11 93Lic B: 0.081 N: 0.42 H(2): 0.315 H: 0.019 14 N B(Mes)2 (Mes)2B N chemical oxidation ESR / 233 ENDOR / 190 electrochemistry, MO calculations [C40H70B2N2] •− •− (Cy)2B N chemical reduction 2.0034 THF 11 92Lic B: 0.24 N: 0.805 H(2): 0.24 14 N B(Cy)2 ESR / 300 electrochemistry, MO calculations [C40H108Ga4Si12] •− C(SiMe3)3 Ga (Me3Si)3C Ga •− electrochemically generated 2.0023 THF 69 96Haa Ga: 1.93 Ga: 2.45 71 ESR / 280 Ga C(SiMe3)3 Ga (Me3Si)3C [C41H36O2Tl] • chemical reaction • tBu O TlPh2 Ph3C O pyridine 88Ste2 203,205 Tl: 1.525 ENDOR / 295 THF 203,205 Tl: 1.780 ENDOR / 295 toluene ENDOR / 295 Landolt-Börnstein New S eries II/ 26A2 203,205 Tl: 2.320 312 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [Ref. p. 329 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C42H48B2] •− chemical reduction 2.0024 92Lic THF 11 •− (Mes)2B B(Mes)2 ESR / 300 B: 0.3 H(2): 0.119 H: 0.029 ENDOR / 180 electrochemistry, MO calculations [C42H60GaO6]3 • 3• tBu O Ga chemical reaction 2.003 toluene 69,71 ESR / 77 O 3 tBu 93Oza Ga: present (theoretical simulation of triradical EPR spectrum) g = 4 (∆M = 2) g = 6 (∆M = 3) crystal structure, magnetic susceptibility [C42H60GaO6]3 • toluene 3• tBu O Ga O tBu 3 2.005 94Lan ESR / 298 toluene 2.003 ESR / 77 69,71 Ga: 0.74 (theoretical simulation of triradical EPR spectrum) g = 4.001 (∆M = 2) g = 6.032 (∆M = 3) crystal structure, magnetic susceptibility [C44H28ClGaN4] •− electrolysis [Ga(TPP)Cl] •− dichloromethane ~ 2.00 85Kad1 ESR / 115 electrochemistry, UV-VIS spectroscopy [C44H28ClGaN4] •+ electrolysis [Ga(TPP)Cl] •+ dichloromethane 85Kad1 69,71 Ga: 1.0 ESR / 298 electrochemistry, UV-VIS spectroscopy Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes 313 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C44H28ClInN4] •+ electrolysis 2.003 85Kad2 [In(TPP)Cl] •+ dichloromethane 115 In: 1.41 ESR / 298 electrochemistry, UV-VIS spectroscopy [C46H33InN4] •− irradiation 2.004 [In(TPP)Et] •− THF 115 89Kad1 In: 1.05 ESR / 300 electrolysis g⊥ = 2.002 THF g|| = 1.968 89Kad1 ESR / 115 electrochemistry [C46H52B2N2] •− •− (Mes)2B N N B(Mes)2 chemical reduction 2.0027 THF 11 ESR / 300 ENDOR / 200 92Lic B: 0.2 H(2): 0.085 H(3): 0.085 H: 0.023 H: 0.014 electrochemistry, MO calculations [C46H52B2N2] •+ •+ (Mes)2B N N B(Mes)2 chemical oxidation 2.0030 92Lic dichloromethane 11 93Lic ESR / 300 ENDOR / 220 B: 0.016 H(2): 0.225 H(3): 0.083 H: 0.011 electrochemistry, MO calculations, UV-VIS spectroscopy Landolt-Börnstein New S eries II/ 26A2 314 3.14 Complexes of group 13 (B, Al, Ga, In, Tl) [Ref. p. 329 Substance Generation / Matrix or Solvent / Method / T [K] g-Factor / a-Value [mT] Ref. / add. Ref. [C48H48AlClN8] •+ electrochemically generated 2.0016 89Fre tBu •+ Cl tBu ESR / 298 N N N N acetonitrile N Al N N N tBu electrochemistry, UV-VIS and NIR spectroscopy tBu [C48H52B2] •− •− (Mes)2B B(Mes)2 chemical reduction 2.0027 THF 11 ESR / 300 ENDOR / 220 92Lic B: 0.2 H(2): 0.085 H(3): 0.085 H: 0.023 H: 0.014 MO calculations [C51H78GaN3O3] •+ •+ electrochemically generated 2.0041 acetonitrile 69 97Ada Ga: 0.230 Ga: 0.290 H(3 H): 0.230 71 N ESR / 298 O N benzyl-deuterated (d6) Ga N O O 69 Ga: 0.230 Ga: 0.290 D(3 D): 0.035 71 tBu tBu tBu N O = tBu O N electrochemistry, UV-VIS spectroscopy, magnetic susceptibility Landolt-Börnstein New S eries II/ 26A2 Ref. p. 329] 3 Radicals in metal complexes Substance Generation / Matrix or Solvent / Method / T [K] [C60H92Ga2] •− chemical reduction R Ga R •− R Ga R THF 315 g-Factor / a-Value [mT] Ref. / add. Ref. 93He 69 Ga: 3.54 Ga: 4.39 H(3): 0.085 71 ESR / 298 iPr R= iPr iPr crystal structure, UV-VIS spectroscopy [C84H117AlN3O6]3 • tBu chemical reduction 3• tBu THF ESR / 298 tBu Al O 3 D = 39.0 mT [C84H117GaN3O6]3 • chemical reduction 3• tBu O tBu N Ga O 3 tBu Landolt-Börnstein New S eries II/ 26A2 Al: 0.42 N: 0.47 H(3): 0.28 H(7): 0.33 H(9): 0.21 D = 16.0 mT tBu tBu 27 14 O N 89Kar 89Kar toluene D = 15.5 mT ESR / 77 D = 30.0 mT
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