Synthesis and Coordination Chemistry of Fluorinated Cyclopentadienyl Ligands

Abstract

The incorporation of fluorinated substituents in cyclopentadienyl anions leads to distinct changes in the properties of the corresponding metal complexes, e.g., with regards to electrochemical properties or metal–ligand bonding energies. This review summarizes the synthetic challenges of the preparation and coordination of fluorinated cyclopentadienyl anions.

1 Introduction

2 Fluorinated Cyclopentadienyls

3 Cyclopentadienyls with One CF₃ Group

4 Cyclopentadienyls with Four CF₃ Groups

5 Cyclopentadienyls with Five CF₃ Groups

6 Cyclopentadienyls with ‘Fluorous Ponytails’

7 Cyclopentadienyls with C₆F₅ Groups

8 Trends in Interaction Energies

9 Conclusion

Key words

cyclopentadienes - fluorine - ligands - metallocenes - substituent effect - transition metals

Publication History

Received: 20 January 2023

Accepted after revision: 06 February 2023

Article published online:
28 February 2023

• References

• 1 Horváth IT, Rábai J. Science 1994; 266: 72
• 2 Hedberg FL, Rosenberg H. J. Organomet. Chem. 1971; 28: C14
• 3 Popov VI, Lib M, Haas A. Ukr. Khim. Zh. 1990; 56: 1115
• 4 Sünkel K, Weigand S. Inorg. Chim. Acta 2011; 370: 224
• 5 Bulfield D, Maschke M, Lieb M, Metzler-Nolte N. J. Organomet. Chem. 2015; 797: 125
• 6 Tazi M, Hedidi M, Erb W, Halauk YS. o, Ivashkevich OA, Matulis VE, Roisnel T, Dorcet V, Bentabed-Ababsa G, Mongin F. Organometallics 2018; 37: 2207
• 7 Tazi M, Erb W, Roisnel T, Dorcet V, Mongin F, Low PJ. Org. Biomol. Chem. 2019; 42: 9352
• 8 Inkpen MS, Du S, Hildebrand M, White AJ. P, Harrison NM, Albrecht T, Long NJ. Organometallics 2015; 34: 5461
• 9 Erb W, Roisnel T. Chem. Commun. 2019; 55: 9132
• 10 Erb W, Roisnel T. Dalton Trans. 2021; 50: 16483
• 11 Sünkel K, Weigand S, Hoffmann A, Blomeyer S, Reuter CG, Vishnevskiy YV, Mitzel NW. J. Am. Chem. Soc. 2015; 137: 126
• 12 Klein-Heßling C, Blockhaus T, Sünkel K. J. Organomet. Chem. 2021; 943: 121833
• 13 Sünkel K, Klein-Heßling C. J. Chem. Cryst. 2022; 52: 131
• 14 Curnow OJ, Hughes RP. J. Am. Chem. Soc. 1992; 114: 5895
• 15 Hughes RP, Zheng X, Ostrander RL, Rheingold AL. Organometallics 1994; 13: 1567
• 16 Hughes RP, Zheng X, Morse CA, Curnow OJ, Lomprey JR, Rheingold AL, Yap GP. A. Organometallics 1998; 17: 457
• 17 Sünkel K, Weigand S, Hoffmann A, Blomeyer S, Reuter CG, Vishnevskiy YV, Mitzel NW. J. Am. Chem. Soc. 2015; 137: 126
• 18 Erb W, Richy N, Hurvois JP, Low PJ, Mongin F. Dalton Trans. 2021; 50: 16933
• 19 Thrasher JS, Seppelt K. J. Fluor. Chem. 1983; 23: 453
• 20 Paprott G, Lentz D, Seppelt K. Chem. Ber. 1984; 117: 1153
• 21 Paprott G, Seppelt K. J. Am. Chem. Soc. 1984; 106: 4060
• 22 Paprott G, Lehmann S, Seppelt K. Chem. Ber. 1988; 121: 727
• 23 Han YH, Heeg MJ, Winter CH. Organometallics 1994; 13: 3009
• 24 Hedberg FL, Rosenberg H. J. Am. Chem. Soc. 1973; 95: 870
• 25 Rupf SM, Dimitrova IS, Schröder G, Malischewski M. Organometallics 2022; 41: 1261
• 26 Winter CH. In Gov. Rep. Announce Index (U.S.), Vol. 96, Abstr. No. 19-00 1996; 125, 276161
• 27 Gassman PG, Winter CH. J. Am. Chem. Soc. 1986; 108: 4228
• 28 Olsson T, Wennerström O. Acta Chem. Scand., Ser. B 1978; 32: 293
• 29 Kucht A, Kucht H, Song W, Rausch MD, Chien JC. W. Appl. Organomet. Chem. 1994; 8: 437
• 30 Werner H, Mahr J, Hörlin G. Z. Anorg. Allg. Chem. 1989; 577: 283
• 31 Cheong M, Basolo F. Organometallics 1988; 7: 2041
• 32 Hal C, Harris JL, Killey A, Maddox TP, Palmer S, Perutz RN, Rooney AD, Goff SE. J, Kazarian SG, Poliakoff M. J. Chem. Soc., Dalton. Trans. 1994; 23: 3515
• 33 Boardman LD, Newmark RA. Magn. Reson. Chem. 1992; 30: 481
• 34 Kruck T, Terfloth C. Chem. Ber. 1993; 126: 1101
• 35 Gassman PG, Michelson JW, Sowa JR. Jr. Inorg. Synth. 1996; 31: 232
• 36 Gassman PG, Sowa JR. Jr, Hill MG, Mann KR. Organometallics 1995; 14: 4879
• 37 O’Connor JM, Baldridge KK, Cope S, Holland RL. Polyhedron 2019; 157: 406
• 38 Barthel-Rosa LP, Sowa JR, Gassman PG, Fischer J, McCarty BM, Goldsmith SL, Gibson MT, Nelson JH. Organometallics 1997; 16: 1595
• 39 Gusev OV, Ievlev MA, Lyssenko KA, Petrovskii PV, Ustynyuk NA, Maitlis PM. Inorg. Chim. Acta 1998; 280: 249
• 40 Paulson ER, Moore CE, Rheingold AL, Pullman DP, Sindewald RW, Cooksy AL, Grotjahn DB. ACS Catal. 2019; 9: 7217
• 41 Qin P, Cope SK, Steger H, Veccharelli KM, Holland RL, Hitt DM, Moore CE, Baldridge KK, O’Connor JM. Organometallics 2017; 36: 3967
• 42 Marken F, Marx HW, Englert U. Struct. Chem. 1994; 5: 177
• 43 Safronov SV, Osipova ES, Nelyubina YV, Filippov OA, Barakovskaya IG, Belkova NV, Shubina ES. Molecules 2020; 25: 2236
• 44 Kerzina ZA, Rybinskaya MI, Dolgushin FM, Yanovsky AI, Petrovskii PV, Kolehmainen E. Izv. Akad. Nauk SSSR, Ser. Khim. (Russ.Chem.Bull.) 1998; 507
• 45 Zhang P, Guo YJ, Chen J, Zhao Y.-R, Chang J, Junge H, Beller M, Li Y. Nat. Catal. 2018; 1: 332
• 46 Janulis EP, Arduengo AJ. III. J. Am. Chem. Soc. 1983; 105: 3563
• 47 Burk MJ, Arduengo AJ. III, Calabrese JC, Harlow RL. J. Am. Chem. Soc. 1989; 111: 8938
• 48 Burk MJ, Calabrese JC, Davidson F, Harlow RL, Roe DC. J. Am. Chem. Soc. 1991; 113: 2209
• 49 Inés B, Holle S, Bock DA, Alcarazo M. Synlett 2014; 25: 1539
• 50 Holle S, Escudero D, Inés B, Rust J, Thiel W, Alcarazo M. Chem. Eur. J. 2015; 21: 2744
• 51 Dickson RS, Wilkinson G. Chem. Ind. (London) 1963; 1432
• 52 Janulis EP, Wilson SR, Arduengo AJ. III. Tetrahedron Lett. 1984; 25: 405
• 53 Davidson JL, Wilson WF, Muir KW. J. Chem. Soc., Chem. Commun. 1985; 460
• 54 Laganis ED, Lemal DM. J. Am. Chem. Soc. 1980; 102: 6633
• 55 Chambers RD, Mullins SJ, Roche AJ, Vaughan JF. S. J. Chem. Soc., Chem. Commun. 1995; 841
• 56 Chambers RD, Roche AJ, Vaughan JF. S. Can. J. Chem. 1996; 74: 1925
• 57 Alberto R., personal communication 2022.
• 58 Chambers RD, Gray WK, Vaughan JF. S, Korn SR, Médebielle M, Batsanov AS, Lehmann CW, Howard JA. K. J. Chem. Soc., Perkin Trans. 1 1997; 135
• 59 Sievers R, Sellin M, Rupf SM, Parche J, Malischewski M. Angew. Chem. Int. Ed. 2022; e202211147
• 60 Brezinski MM, Klabunde J, Janikowski SK, Radanovich LJ. Inorg. Chem. 1985; 24: 3305
• 61 Slocum DW, Engelmann TR, Fellows RL, Morosnki M, Duraj S. J. Organomet. Chem. 1984; 260: C21
• 62 Shore SG, Hsu WL, Churchill MR, Bueno C. J. Am.Chem. Soc. 1983; 105: 655
• 63 Čermák J, Auerová K, Nguyen HT. T, Blechta V, Vojtíšek P, Kvíčala J. Collect. Czech. Chem. Commun. 2001; 66, 382
• 64 Čermák J, Žádný J, Krupková A, Lopatová K, Vlachová A, Thi TH. N, Šauliová J, Sýkora J, Císařová I. J. Organomet. Chem. 2007; 692: 1557
• 65 Čermák J, Krupková A, Auerová K, Zamrzla M, Thi TH. N, Vojtíšek P, Císařová I. J. Organomet. Chem. 2010; 695: 375
• 66 Hughes RP, Husebo TL, Maddock SM, Rheingold AL, Guzei IA. J. Am. Chem. Soc. 1997; 119: 10231
• 67 Hughes RP, Maddock SM, Guzei IA, Liable-Sands LM, Rheingold AL. J. Am. Chem. Soc. 2001; 123: 3279
• 68 Hughes RP, Trujillo HA. Organometallics 1996; 15: 286
• 69 Bříza T, Kvíčala J, Paleta O, Čermák J. Tetrahedron 2002; 58: 3841
• 70 Bříza T, Kvíčala J., Mysík P., Paleta O, Čermák J. Synlett 2001; 685
• 71 Dinh LV, Gladysz JA. Chem. Commun. 2004; 998
• 72 Dinh LV, Gladysz JA. Chem. Eur. J. 2005; 11: 7211
• 73 Gladysz JA, Curran DP, Horváth IT. Handbook of Fluorous Chemistry. Wiley-VCH; Weinheim: 2004
• 74 Deck PA. Coord. Chem. Rev. 2006; 250: 1032
• 75 Deck PA, Jackson WF, Fronczek FR. Organometallics 1996; 15: 5287
• 76 Thornberry MP, Slebodnick C, Deck PA, Fronczek FR. Organometallics 2001; 20: 920
• 77 Becke S, Denninger U, Kahlert S, Obrecht W, Schmid C, Windisch H. WO9915534 1999
• 78 Schulte Y, Schulz S. In 21st Conference of Inorganic Chemistry. Marburg: Germany 2022
• 79 Thornberry MP, Slebodnick C, Deck PA, Fronczek FR. Organometallics 2000; 19: 5352