Scorpionates Ii: Chelating Borate Ligands - Dedicated To Swiatoslaw Trofimenko Dedicated to Swiatoslaw Trofimenko

Since their discovery by Swiatoslaw Trofimenko in 1967, poly(pyrazol-1-yl)borates have been considered as one of the most useful ligands in modern coordination chemistry. The term scorpionate has been used to describe the interchange between bidentate and tridentate coordination modes by these ligands that has been employed for the synthesis of complexes with virtually every metal in the periodic table, having applications in diverse fields ranging from homogeneous catalysis to bioinorganic chemistry. This all-inclusive reference book continues where Trofimenko's original work left off. It not only includes discussions on all new ligands reported from 1999 to date, but also introduces new ligands that have yet to be touched upon in other titles, such as scorpionates based on S donors or P donors. As such, this comprehensive volume is a must have for all researchers who utilize this family of molecules. Contents: Homoscorpionates -- First Generation; Homoscorpionates -- Second Generation; Heteroscorpionates; Scorpionates Based on Thioimidazolones as Sulfur Donors and Related Ligands; Scorpionates Based on Thioethers as Sulfur Donors; Scorpionates Based on Diaryl or Dialkylphosphine as Donors; Application; Concluding Remarks. Contents......Page 18 Foreword......Page 8 Jerry Tro.menko: A Testimonial......Page 10 Acknowledgments......Page 16 1.1 General Considerations......Page 23 1.2 Scorpionate Ligands: Abbreviation System......Page 27 1.3 Scorpionate (poly(pyrazolyl)borate) Features......Page 29 1.4 Scorpionate Coordination Mode......Page 36 1.5 Reviews......Page 37 1.6 Synthesis of Scorpionate Ligands......Page 41 1.7 Regiochemistry......Page 43 1.8.3. Tp4tBu, TpTol,4tBu, and TpiPr,4tBu......Page 45 1.8.4. Tp(2,4(OMe)2Ph) and Bp(2,4(OMe)2Ph)......Page 46 1.8.6. TpFu,Me......Page 47 1.8.8. TpBn,Me and TpBn,4Ph......Page 48 1.8.11. TpBr3......Page 49 1.8.13. TpBr,Ph,Br, TpBr,p-Tol,Br, TpBr,p-ClPh,Br , Tpp-ClPh,4Br , and TpPh,Me,Br......Page 51 1.8.15. TpαNt and TpβNt......Page 52 1.8.17. Tp4py, Bp4py, pz0Tp4py, Bp3py, Tp3py, and pz0Tp3py......Page 53 1.8.20. Bp2pyr......Page 54 1.8.21. Tp(4py),Me, Tp(4-(2-Mepy),Me, Tp(CONHPh),Me, and Tp(CONHC(Me3),Me......Page 55 1.8.22. Tp2(6Me)py......Page 56 1.8.24. Bp4CN and BpPh,4CN......Page 57 1.8.25. Tp4Bo,6-COOEt and Tp4Bo,6-CH2SEt......Page 58 1.8.26. pzTpcamph, TpCH2N(Me)EtPh, (BBN)Bp+/-camph, and (BBN)Bp+menthone......Page 59 1.8.28. TpCO2Et,Me......Page 60 1.8.29. BpCO2Et,Me......Page 61 1.8.31. PhTptBu......Page 62 1.8.32. tBuTpR (R=H, Me, iPr, tBu, Ph) and tBuBp......Page 63 1.8.34. MeTpx (Tpx = Tp, Tp or TpMe)......Page 64 1.8.36. CymTp, Cym Tp, and Cym TpR Tl (R=CH2(C6H11))......Page 65 1.8.38. IpcTp......Page 66 1.8.41. MeTp(C2F5)3......Page 67 1.8.42. Ph2BpR,R......Page 68 1.8.44.1. (p-IC6H4)TpR (R = H or Me)......Page 69 1.8.44.3. p-BrC6H4Tp, p-(HO2C)C6H4Tp, and p-( tBuO-Phe-CO)C6H4Tp......Page 70 1.8.44.4. (pz)3CCH2OCH2–C2–C6H4Tp and {3,5-[(pz)3CCH2OCH2]2C6H3C2}C6H4Tp......Page 71 1.8.47. 1,1 -fc(BMe2pz)2......Page 73 1.8.49. [1,n-(tBuBp)2C6H4], [1,4-(Tp)2C6H4], and [(Bp)2(C6H4)2]......Page 74 1.8.50. {CH2=CHCH2Bp(CH2PPh2)}, {CH2=CHCH2Tp}, and their carbosilane dendrimer......Page 75 1.8.52. H2B(tz)2......Page 77 1.8.55. {HB(pzPh,Me)(mt(2,6-Me2Ph))2}......Page 78 1.8.56. [MeB(ImN-Me)2(pzx)]......Page 79 References......Page 80 2.2.2. Na......Page 90 2.3.1. Mg......Page 91 2.4.2. Y......Page 92 2.5.1. Ti......Page 93 2.5.2. Zr......Page 95 2.5.3. Hf......Page 97 2.6.1. V......Page 98 2.6.2. Nb......Page 100 2.6.3. Ta......Page 103 2.7.1. Cr......Page 104 2.7.2. Mo......Page 105 2.7.3. W......Page 125 2.8.1. Mn......Page 144 2.8.2. Re......Page 145 2.9.1. Fe......Page 154 2.9.2. Ru......Page 161 2.9.3. Os......Page 189 2.10.1. Co......Page 196 2.10.2. Rh......Page 198 2.10.3. Ir......Page 210 2.11.1. Ni......Page 222 2.11.2. Pd......Page 225 2.11.3. Pt......Page 229 2.12.1. Cu......Page 238 2.12.2. Ag......Page 241 2.12.3. Au......Page 243 2.13.1. Zn......Page 245 2.13.2. Cd......Page 246 2.14.2. In......Page 247 2.15.2. Sn......Page 249 2.16.1. Bi......Page 250 2.17.1. La......Page 251 2.17.4. Nd......Page 252 2.17.5. Sm......Page 254 2.17.6. Eu......Page 259 2.17.7. Gd......Page 260 2.17.8. Tb......Page 261 2.17.12. Yb......Page 262 2.17.13. Lu......Page 264 2.18.1. U......Page 265 References......Page 267 3.2 Tp4Me......Page 297 3.5 TpBr (゚ TpMe2Br)......Page 298 3.7 TpEt......Page 299 3.9 TpiPr......Page 300 3.10 pz0TpiPr......Page 302 3.12 TpiPr2......Page 303 3.14 Tp4Br......Page 315 3.16 pz0TptBu......Page 316 3.19 TptBu,Me......Page 317 3.20 TptBu,iPr......Page 324 3.21 TpPh......Page 325 3.23 TpPhCl......Page 329 3.24 TpPh,Me......Page 330 3.25 TpPh2......Page 336 3.27 TpMs and TpMs......Page 338 3.29 TpCum,Me......Page 342 3.31 TpTn......Page 347 3.33 TpAn......Page 348 3.34 TpAn,Me......Page 350 3.37 TpCF3......Page 351 3.38 TpCF3,Me......Page 352 3.39 Tp(CF3)2......Page 353 3.41 MeTpCF3......Page 356 3.42 Tp4Bo......Page 357 3.45 TpBo4Me,7iPr......Page 358 3.46 pz0TpCpr and TpCpr......Page 359 3.47 Tppy......Page 360 3.49 Tppy......Page 361 3.53 TpMenth and TpMementh......Page 363 3.55 HB(tz)3......Page 364 References......Page 366 4.2.1. Bpx......Page 378 4.2.1.1. Bp and Bp......Page 379 4.2.1.3. Bp tBu......Page 384 4.2.1.6. BpPh......Page 385 4.2.1.7. Bp2py......Page 386 4.2.1.9. Bp(CF3)2......Page 387 4.2.2.1. Et2Bp......Page 389 4.2.2.2. Ph2Bp......Page 390 4.2.3.1. H2B(pz4Me)(pz)......Page 391 4.2.4.1. (pzPh2 )Bp and (pz)BpPh2......Page 392 4.2.4.3. (pz5- iPr)BpPh,Me and (pz5- iPr)BpPh2......Page 393 4.2.4.5. (pz)BpPh,Me and (pzMe,Ph)BpPh,Me......Page 394 4.2.4.7. (pz)BptBu2......Page 395 4.2.4.11. (mttBu)Bp......Page 396 4.4 H2B(Az)2 (Az=tz or btz)......Page 397 References......Page 399 5.1.1. TmMe(゚ Tm) derivatives......Page 403 5.1.2. TmPh......Page 411 5.1.3. TmtBu......Page 413 5.1.4. TmCum......Page 414 5.1.5. Tmp-T ol......Page 415 5.1.8. TmXyl......Page 416 5.1.10. MeimTmαMeBn......Page 417 5.2.1. BmMe(≡Bm) derivatives......Page 418 5.2.3. BmR(R = Bn, tBu, p-Tol)......Page 421 5.2.5. [(pzPh,Me)BmR] (R = o-An, Cum, Xyl)......Page 422 5.2.7. PhBm......Page 423 5.4 Thioxotriazolylborates (゚ TrR)......Page 424 5.6 Tdz......Page 425 5.5 Tz and Tbz......Page 21 5.7 [BseMe], [TseMe], and [TseMs]......Page 426 5.8 mtRBp......Page 427 5.10 Metallaboratranes: M → B(mt)3......Page 428 References......Page 432 6.1 {B(CH2SCH3)4} (゚ RTt)......Page 438 6.2 {B(C4H3S)4} (゚ RTtTn)......Page 439 6.4 {PhB(CH2S(tBu))3} (゚ PhTttBu)......Page 440 6.8 {Ph(pztBu)BttBu}......Page 443 6.12 {Et2B(CH2SCH3)2} (゚ Et2Bt)......Page 444 References......Page 445 7.1.1. PhBP3(゚ PhBPPh3)......Page 447 7.1.2. PhBPiPr......Page 452 7.2.1. Ph2BP2(゚ Ph2BPPh2 )......Page 455 7.2.3. Other dialkyl- and diarylphosphino-borates......Page 458 References......Page 459 8.1 General Considerations......Page 461 8.2.1. Polymerization and oligomerization......Page 462 8.2.2. Carbene and nitrene transfer......Page 466 8.2.3. Oxidation......Page 471 8.2.4. Miscellaneous catalysis......Page 473 8.3 Enzyme Modeling......Page 475 8.3.3. Tungsten......Page 476 8.3.5. Iron......Page 477 8.3.8. Copper......Page 478 8.3.9. Zinc......Page 480 8.4 C–H Activation......Page 483 8.5 New Materials......Page 491 8.6 Metal Extraction......Page 496 8.7 Miscellaneous Studies......Page 497 References......Page 499 9 Concluding Remarks......Page 511 References......Page 512 Appendix......Page 515 Abbreviations......Page 562 Index......Page 567 "Since their discovery by Swiatoslaw Trofimenko in 1967, poly(pyrazol-1-yl)borates have been considered as one of the most useful ligands in modern coordination chemistry. The term "scorpionate" has been used to describe the interchange between bidentate and tridentate coordination modes by these ligands that has been employed for the synthesis of complexes with virtually every metal in the periodic table, having applications in diverse fields ranging from homogeneous catalysis to bioinorganic chemistry." "This all-inclusive reference book continues where Trofimenko's original work left off. It not only includes discussions on all new ligands reported from 1999 to date, but also introduces new ligands that have yet to be touched upon in other titles, such as scorpionates based on S donors or P donors. As such, this comprehensive volume is a "must have" for all researchers who utilize this family of molecules."--BOOK JACKET Since their discovery by Swiatoslaw Trofimenko in 1967, poly(pyrazol-1-yl) borates have been considered as one of the most useful ligands in modern coordination chemistry. The term "scorpionate" has been used to describe the interchange between bidentate and tridentate coordination modes by these ligands that has been employed for the synthesis of complexes with virtually every metal in the periodic table, having applications in diverse fields ranging from homogeneous catalysis to bioinorganic chemistry. This all-inclusive reference book continues where Trofimenko's original work left off. It not only includes discussions on all new ligands reported from 1999 to date, but also introduces new ligands that have yet to be touched upon in other titles, such as scorpionates based on S donors or P donors. As such, this comprehensive volume is a "must have" for all researchers who utilize this family of molecules