Metallole

Metalloles are metallacycle derivatives of cyclopentadiene in which the carbon atom at position 5, the saturated carbon, is replaced by a heteroatom.^[1] In contrast to its parent compound, the numbering of the metallole starts at the heteroatom. Some of these compounds are described as organometallic compounds, but in the list below quite a number of metalloids are present too. Some metalloles are fluorescent.^[2] Polymeric derivatives of pyrrole and thiophene are of interest in molecular electronics. Metalloles, which can also be viewed as structural analogs of pyrrole, include:

Calculated geometry and inversion barrier energy E for some C₄H₄MH metalloles^[3]
Name	M	d(M-C), Å	d(M-H), Å	α(C-M-C), °	E, kJ/mol
Pyrrole	N	1.37	1.01	110	0
Phosphole	P	1.81	1.425	90.5	67
Arsole	As	1.94	1.53	86	125
Stibole	Sb	2.14	1.725	80.5	160
Bismole	Bi	2.24	1.82	78	220

Arsole, a moderately-aromatic arsenic analog
Bismole, a bismuth analog
Borole, a boron analog
Furan (oxole), an oxygen analog
Gallole, a gallium analog
Germole, a germanium analog
Phosphole, a phosphorus analog
Pyrrole (azole), a nitrogen analog
Selenophene, a selenium analog
Silole, a silicon analog
Stannole, a tin analog
Stibole, an antimony analog
Tellurophene, a tellurium analog
Plumbole,^[4]^[5] a lead analog
Thiophene, a sulfur analog
Titanacyclopentadiene, e.g. (C₅H₅)₂TiC₄Ph₄^[6]
Zirconacyclopentadiene, e.g. (C₅H₅)₂ZrC₄Ph₄^[7]
Ferrole, an iron analog

Structure of the ferrole complex Fe₂(C₄H₄)(CO)₆.^[8]

References

^ Dubac, Jacques; Laporterie, Andre; Manuel, Georges (1990). "Group 14 Metalloles. 1. Synthesis, Organic Chemistry, and Physicochemical Data". Chemical Reviews. 90: 215–263. doi:10.1021/cr00099a008.
^ Tracy, Henry J.; Mullin, Jerome L.; Klooster, Wim T.; Martin, James A.; Haug, Judith; Wallace, Scott; Rudloe, Isaac; Watts, Kimberly (2005). "Enhanced Photoluminescence from Group 14 Metalloles in Aggregated and Solid Solutions". Inorganic Chemistry. 44 (6): 2003–2011. doi:10.1021/ic049034o. PMID 15762727.
^ Pelzer, Silke; Wichmann, Karin; Wesendrup, Ralf; Schwerdtfeger, Peter (2002). "Trends in Inversion Barriers IV. The Group 15 Analogous of Pyrrole". The Journal of Physical Chemistry A. 106 (26): 6387. Bibcode:2002JPCA..106.6387P. doi:10.1021/jp0203494.
^ Saito, Masaichi; Nakada, Marisa; Kuwabara, Takuya; Owada, Ryota; Furukawa, Shunsuke; Narayanan, Radhika; Abe, Minori; Hada, Masahiko; Tanaka, Ken; Yamamoto, Yoshihiko (2019-08-26). "Inverted Sandwich Rh Complex Bearing a Plumbole Ligand and Its Catalytic Activity". Organometallics. 38 (16): 3099–3103. doi:10.1021/acs.organomet.9b00339. ISSN 0276-7333.
^ Münzfeld, Luca; Sun, Xiaofei; Schlittenhardt, Sören; Schoo, Christoph; Hauser, Adrian; Gillhuber, Sebastian; Weigend, Florian; Ruben, Mario; Roesky, Peter W. (2021-12-10). "Introduction of plumbole to f-element chemistry". Chemical Science. 13 (4): 945–954. doi:10.1039/D1SC03805B. ISSN 2041-6539. PMC 8790777. PMID 35211259.
^ Atwood, Jerry L.; Hunter, William E.; Alt, Helmut; Rausch, Marvin D. (1976). "The molecular structure of 1,1-bis(.eta.5-cyclopentadienyl)-2,3,4,5-tetraphenyltitanole and its hafnium analogue". Journal of the American Chemical Society. 98 (9): 2454–2459. Bibcode:1976JAChS..98.2454A. doi:10.1021/ja00425a012.
^ Urrego-Riveros, Sara; Ramirez y Medina, Isabel-Maria; Duvinage, Daniel; Lork, Enno; Sönnichsen, Frank D.; Staubitz, Anne (2019). "Negishi's Reagent Versus Rosenthal's Reagent in the Formation of Zirconacyclopentadienes". Chemistry – A European Journal. 25 (58): 13318–13328. doi:10.1002/chem.201902255. PMC 6851999. PMID 31347203.
^ Dettlaf G, Weiss E (1976). "Kristallstruktur, ¹H-NMR- und Massenspektrum von Tricarbonylferracyclopentadien-tricarbonyleisen, C₄H₄Fe₂(CO)₆" [Crystal Structure, Proton NMR and Mass Spectrum of Tricarbonylferracyclopentadienetricarbonyliron, C₄H₄Fe₂(CO)₆]. J. Organomet. Chem. 108 (2): 213–23. doi:10.1016/S0022-328X(00)82143-9.

[1] Dubac, Jacques; Laporterie, Andre; Manuel, Georges (1990). "Group 14 Metalloles. 1. Synthesis, Organic Chemistry, and Physicochemical Data". Chemical Reviews. 90: 215–263. doi:10.1021/cr00099a008.

[2] Tracy, Henry J.; Mullin, Jerome L.; Klooster, Wim T.; Martin, James A.; Haug, Judith; Wallace, Scott; Rudloe, Isaac; Watts, Kimberly (2005). "Enhanced Photoluminescence from Group 14 Metalloles in Aggregated and Solid Solutions". Inorganic Chemistry. 44 (6): 2003–2011. doi:10.1021/ic049034o. PMID 15762727.

[geo-3] Pelzer, Silke; Wichmann, Karin; Wesendrup, Ralf; Schwerdtfeger, Peter (2002). "Trends in Inversion Barriers IV. The Group 15 Analogous of Pyrrole". The Journal of Physical Chemistry A. 106 (26): 6387. Bibcode:2002JPCA..106.6387P. doi:10.1021/jp0203494.

[4] Saito, Masaichi; Nakada, Marisa; Kuwabara, Takuya; Owada, Ryota; Furukawa, Shunsuke; Narayanan, Radhika; Abe, Minori; Hada, Masahiko; Tanaka, Ken; Yamamoto, Yoshihiko (2019-08-26). "Inverted Sandwich Rh Complex Bearing a Plumbole Ligand and Its Catalytic Activity". Organometallics. 38 (16): 3099–3103. doi:10.1021/acs.organomet.9b00339. ISSN 0276-7333.

[5] Münzfeld, Luca; Sun, Xiaofei; Schlittenhardt, Sören; Schoo, Christoph; Hauser, Adrian; Gillhuber, Sebastian; Weigend, Florian; Ruben, Mario; Roesky, Peter W. (2021-12-10). "Introduction of plumbole to f-element chemistry". Chemical Science. 13 (4): 945–954. doi:10.1039/D1SC03805B. ISSN 2041-6539. PMC 8790777. PMID 35211259.

[6] Atwood, Jerry L.; Hunter, William E.; Alt, Helmut; Rausch, Marvin D. (1976). "The molecular structure of 1,1-bis(.eta.5-cyclopentadienyl)-2,3,4,5-tetraphenyltitanole and its hafnium analogue". Journal of the American Chemical Society. 98 (9): 2454–2459. Bibcode:1976JAChS..98.2454A. doi:10.1021/ja00425a012.

[7] Urrego-Riveros, Sara; Ramirez y Medina, Isabel-Maria; Duvinage, Daniel; Lork, Enno; Sönnichsen, Frank D.; Staubitz, Anne (2019). "Negishi's Reagent Versus Rosenthal's Reagent in the Formation of Zirconacyclopentadienes". Chemistry – A European Journal. 25 (58): 13318–13328. doi:10.1002/chem.201902255. PMC 6851999. PMID 31347203.

[8] Dettlaf G, Weiss E (1976). "Kristallstruktur, ¹H-NMR- und Massenspektrum von Tricarbonylferracyclopentadien-tricarbonyleisen, C₄H₄Fe₂(CO)₆" [Crystal Structure, Proton NMR and Mass Spectrum of Tricarbonylferracyclopentadienetricarbonyliron, C₄H₄Fe₂(CO)₆]. J. Organomet. Chem. 108 (2): 213–23. doi:10.1016/S0022-328X(00)82143-9.

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Metallole

See also

References