Structure of C60[IrCl(CO)(PMe3)2]2.[1] Color code: green = Cl, blue = Ir, ochre = P
One year after it was prepared in milligram quantities in 1990,[3] C60 was shown to function as a ligand in the complex [Ph3P]2Pt(η2-C60).[4]
Since this report, a variety of transition metals and binding modes were demonstrated. Most transition metal fullerene complex are derived from C60, although other fullerenes also coordinate to metals as seen with C70Rh(H)(CO)(PPh3)2.[5]
As ligands, fullerenes behave similarly to electron-deficientalkenes such as tetracyanoethylene. Thus, their complexes are a subset of metal-alkene complexes. They almost always coordinate in a dihapto fashion and prefer electron-rich metal centers.[6] This binding occurs on the junction of two 6-membered rings. Hexahapto and pentahapto bonding is rarely observed.[7]
In Ru3(CO)9(C60), the fullerene binds to the triangular face of the cluster.[8]
Illustrative Fullerene Complexes
[[Ph3P]2Pt]6(η2-C60)
Ru3(CO)9(C60)
Platinum complex of isoxazoline-modified fullerene.
Examplesedit
C60 forms stable complexes of the type M(C60)(diphosphine)(CO)3 for M = Mo, W. A dirhenium complexes is known with the formula Re2(PMe3)4H8(η2:η2C60) where two of the hydrogen act as bridging ligands.[5]
Many fullerene complexes are derived from platinum metals. An unusual cationic complex features three 16e Ru centers:
Vaska's complex forms a 1:1 adduct, and the analogous IrCl(CO)(PEt3)2 binds 200x more strongly.[2] Complexes with more than one fullerene ligand are illustrated by Ir4(CO)3(μ4-CH)(PMe3)2(μ-PMe)2(CNCH2Ph)(μ-η2:η2C60)(μ4-η1:η1:η2:η2C60). In this Ir4 cluster two fullerene ligands with multiple types of mixed binding. Platinum, palladium, and nickel form complexes of the type C60ML2 where L is a monodentate or bidentate phosphorus ligand.[5] They are prepared by displacement of weakly coordinating ligands such as ethylene:[6]
[Ph3P]2Pt(C2H4) + C60 → [Ph3P]2Pt(η2-C60) + C2H4
In [(Et3P)2Pt]6(η2-C60), six Pt centers are bound to the fullerene.[9]
Modified fullerenes as ligandsedit
Osmium tetraoxide adds to C60 to give, in the presence of pyridine (py), the diolate C60O2OsO2(py)2.[2]
In this example, the binding of the ligand is similar to ferrocene. The anion C60(PhCH2)2Ph functions as an indenyl-like ligand.[10] Fullerenes can also be substituents on otherwise conventional ligands as seen with an isoxazoline fullerene chelating to platinum, rhenium, and iridium compounds.[11]
^Alan L. Balch; Joong W. Lee; Bruce C. Noll; Marilyn M. Olmstead (1994). "Multiple Additions of Vaska-Type Iridium Complexes to C60. Preferential Crystallization of the "Para" Double Addition Products: C60{Ir(CO)Cl(PMe3)2}2.2C6H6 and C60{Ir(CO)Cl(PEt3)2}2.C6H6". Inorg. Chem. 33: 5238–5243. doi:10.1021/ic00101a015.
^ abcAlan L. Balch; Marilyn M. Olmstead (1998). "Reactions of Transition Metal Complexes with Fullerenes (C60, C70, etc.) and Related Materials". Chem. Rev. 98 (6): 2123–2166. doi:10.1021/cr960040e. PMID 11848962.
^Krätschmer, W. (1990). "The infrared and ultraviolet absorption spectra of laboratory-produced carbon dust: evidence for the presence of the C60 molecule". Chemical Physics Letters. 170 (2–3): 167–170. Bibcode:1990CPL...170..167K. doi:10.1016/0009-2614(90)87109-5.
^Fagan, P.J.; Calabrese, J.C.; Malone, B. (1991). "The Chemical Nature of Buckminsterfullerene (C60) and the characterization of a platinum derivative". Science. 252 (5009): 1160–1161. Bibcode:1991Sci...252.1160F. doi:10.1126/science.252.5009.1160. ISSN 0036-8075. JSTOR 2876290. S2CID 95654230.
^ abcdDenisovich, L. I.; Peregudova, S. M.; Novikov, Yu. N. (2010). "Electrochemical properties of transition metal complexes with C60 and C70 fullerene ligands (review)". Russian Journal of Electrochemistry. 46 (1): 1–17. doi:10.1134/S1023193510010015. S2CID 56103986.
^Hsu, Hsiu-Fu; Shapley, John R. (1996). "Ru3(CO)9(μ3-η2,η2,η2-C60): A Cluster Face-Capping, Arene-Like Complex of C60". J. Am. Chem. Soc. 118 (38): 9192. doi:10.1021/ja962077m.
^Fagan, P.J.; Calabrese, J.C.; Malone, B. (1991). "A multiply-substituted buckminsterfullerene (C60) with an octahedral array of platinum atoms". Journal of the American Chemical Society. 113 (24): 9408–9409. doi:10.1021/ja00024a079.
^Toganoh, Motoki; Matsuo, Yutaka; Nakamura, Eiichi (2003). "Synthesis and catalytic activity of rhodium diene complexes bearing indenyl-type fullerene η5-ligand". Journal of Organometallic Chemistry. 683 (2): 295–300. doi:10.1016/S0022-328X(03)00465-0.
^RamíRez-Monroy, Armando; Swager, Timothy M. (2011). "Metal Chelates Based on Isoxazoline[60]fullerenes". Organometallics. 30 (9): 2464–2467. doi:10.1021/om200238a.
^Dragonetti, Claudia; Valore, Adriana; Colombo, Alessia; Righetto, Stefania; Rampinini, Giovanni; Colombo, Francesca; Rocchigiani, Luca; MacChioni, Alceo (2012). "An investigation on the second-order NLO properties of novel cationic cyclometallated Ir(III) complexes of the type [Ir(2-phenylpyridine)2(9-R-4,5-diazafluorene)]+ (R=H, fulleridene) and the related neutral complex with the new 9-fulleriden-4-monoazafluorene ligand". Inorganica Chimica Acta. 382: 72–78. doi:10.1016/j.ica.2011.10.018.
^Santos, Leandro J.; Carvalhoda-Silva, Dayse; Rebouças, Júlio S.; Alves, Marcos R.A.; Idemori, Ynara M.; Matencio, Tulio; Freitas, Rossimiriam P. (2011). "Synthesis of new porphyrin/fullerene supramolecular assemblies: A spectroscopic and electrochemical investigation of their coordination equilibrium in solution". Tetrahedron. 67: 228–235. doi:10.1016/j.tet.2010.10.066.
Bibliographyedit
Spessard, Gary; Miessler, Gary (2010). Organometallic Chemistry ISBN0195330994
April 09, 2024
transition, metal, fullerene, complex, transition, metal, fullerene, complex, coordination, complex, wherein, fullerene, serves, ligand, fullerenes, typically, spheroidal, carbon, compounds, most, prevalent, being, buckminsterfullerene, structure, ircl, pme3, . A transition metal fullerene complex is a coordination complex wherein fullerene serves as a ligand Fullerenes are typically spheroidal carbon compounds the most prevalent being buckminsterfullerene C60 2 Structure of C60 IrCl CO PMe3 2 2 1 Color code green Cl blue Ir ochre POne year after it was prepared in milligram quantities in 1990 3 C60 was shown to function as a ligand in the complex Ph3P 2Pt h2 C60 4 Since this report a variety of transition metals and binding modes were demonstrated Most transition metal fullerene complex are derived from C60 although other fullerenes also coordinate to metals as seen with C70Rh H CO PPh3 2 5 Contents 1 Binding modes 2 Examples 3 Modified fullerenes as ligands 4 Ongoing research 5 See also 6 References 7 BibliographyBinding modes editAs ligands fullerenes behave similarly to electron deficient alkenes such as tetracyanoethylene Thus their complexes are a subset of metal alkene complexes They almost always coordinate in a dihapto fashion and prefer electron rich metal centers 6 This binding occurs on the junction of two 6 membered rings Hexahapto and pentahapto bonding is rarely observed 7 In Ru3 CO 9 C60 the fullerene binds to the triangular face of the cluster 8 Illustrative Fullerene Complexes nbsp Ph3P 2Pt 6 h2 C60 nbsp Ru3 CO 9 C60 nbsp Platinum complex of isoxazoline modified fullerene Examples editC60 forms stable complexes of the type M C60 diphosphine CO 3 for M Mo W A dirhenium complexes is known with the formula Re2 PMe3 4H8 h2 h2C60 where two of the hydrogen act as bridging ligands 5 Many fullerene complexes are derived from platinum metals An unusual cationic complex features three 16e Ru centers 3 Cp Ru MeCN 3 C60 Cp Ru MeCN 2 3C60 3 3 MeCNVaska s complex forms a 1 1 adduct and the analogous IrCl CO PEt3 2 binds 200x more strongly 2 Complexes with more than one fullerene ligand are illustrated by Ir4 CO 3 m4 CH PMe3 2 m PMe 2 CNCH2Ph m h2 h2C60 m4 h1 h1 h2 h2C60 In this Ir4 cluster two fullerene ligands with multiple types of mixed binding Platinum palladium and nickel form complexes of the type C60ML2 where L is a monodentate or bidentate phosphorus ligand 5 They are prepared by displacement of weakly coordinating ligands such as ethylene 6 Ph3P 2Pt C2H4 C60 Ph3P 2Pt h2 C60 C2H4In Et3P 2Pt 6 h2 C60 six Pt centers are bound to the fullerene 9 Modified fullerenes as ligands editOsmium tetraoxide adds to C60 to give in the presence of pyridine py the diolate C60O2OsO2 py 2 2 The pentaphenyl anion C60Ph5 behaves as a cyclopentadienyl ligand 5 nbsp Ferrocene like complex of C60Ph5 In this example the binding of the ligand is similar to ferrocene The anion C60 PhCH2 2Ph functions as an indenyl like ligand 10 Fullerenes can also be substituents on otherwise conventional ligands as seen with an isoxazoline fullerene chelating to platinum rhenium and iridium compounds 11 Ongoing research editAlthough no application has been commercialized non linear optical NLO materials 12 and as supramolecular building blocks 13 See also editExohedral fullerene Endohedral fullereneReferences edit Alan L Balch Joong W Lee Bruce C Noll Marilyn M Olmstead 1994 Multiple Additions of Vaska Type Iridium Complexes to C60 Preferential Crystallization of the Para Double Addition Products C60 Ir CO Cl PMe3 2 2 2C6H6 and C60 Ir CO Cl PEt3 2 2 C6H6 Inorg Chem 33 5238 5243 doi 10 1021 ic00101a015 a b c Alan L Balch Marilyn M Olmstead 1998 Reactions of Transition Metal Complexes with Fullerenes C60 C70 etc and Related Materials Chem Rev 98 6 2123 2166 doi 10 1021 cr960040e PMID 11848962 Kratschmer W 1990 The infrared and ultraviolet absorption spectra of laboratory produced carbon dust evidence for the presence of the C60 molecule Chemical Physics Letters 170 2 3 167 170 Bibcode 1990CPL 170 167K doi 10 1016 0009 2614 90 87109 5 Fagan P J Calabrese J C Malone B 1991 The Chemical Nature of Buckminsterfullerene C60 and the characterization of a platinum derivative Science 252 5009 1160 1161 Bibcode 1991Sci 252 1160F doi 10 1126 science 252 5009 1160 ISSN 0036 8075 JSTOR 2876290 S2CID 95654230 a b c d Denisovich L I Peregudova S M Novikov Yu N 2010 Electrochemical properties of transition metal complexes with C60 and C70 fullerene ligands review Russian Journal of Electrochemistry 46 1 1 17 doi 10 1134 S1023193510010015 S2CID 56103986 a b Spessard p 162 Spessard p 165 Hsu Hsiu Fu Shapley John R 1996 Ru3 CO 9 m3 h2 h2 h2 C60 A Cluster Face Capping Arene Like Complex of C60 J Am Chem Soc 118 38 9192 doi 10 1021 ja962077m Fagan P J Calabrese J C Malone B 1991 A multiply substituted buckminsterfullerene C60 with an octahedral array of platinum atoms Journal of the American Chemical Society 113 24 9408 9409 doi 10 1021 ja00024a079 Toganoh Motoki Matsuo Yutaka Nakamura Eiichi 2003 Synthesis and catalytic activity of rhodium diene complexes bearing indenyl type fullerene h5 ligand Journal of Organometallic Chemistry 683 2 295 300 doi 10 1016 S0022 328X 03 00465 0 RamiRez Monroy Armando Swager Timothy M 2011 Metal Chelates Based on Isoxazoline 60 fullerenes Organometallics 30 9 2464 2467 doi 10 1021 om200238a Dragonetti Claudia Valore Adriana Colombo Alessia Righetto Stefania Rampinini Giovanni Colombo Francesca Rocchigiani Luca MacChioni Alceo 2012 An investigation on the second order NLO properties of novel cationic cyclometallated Ir III complexes of the type Ir 2 phenylpyridine 2 9 R 4 5 diazafluorene R H fulleridene and the related neutral complex with the new 9 fulleriden 4 monoazafluorene ligand Inorganica Chimica Acta 382 72 78 doi 10 1016 j ica 2011 10 018 Santos Leandro J Carvalhoda Silva Dayse Reboucas Julio S Alves Marcos R A Idemori Ynara M Matencio Tulio Freitas Rossimiriam P 2011 Synthesis of new porphyrin fullerene supramolecular assemblies A spectroscopic and electrochemical investigation of their coordination equilibrium in solution Tetrahedron 67 228 235 doi 10 1016 j tet 2010 10 066 Bibliography editSpessard Gary Miessler Gary 2010 Organometallic Chemistry ISBN 0195330994 Retrieved from https en wikipedia org w index php title Transition metal fullerene complex amp oldid 1177943971, wikipedia, wiki, book, books, library,
