JP4636889B2 - FULLERENE DERIVATIVE, FULLERENE METAL COMPLEX, AND METHOD FOR PRODUCING THEM - Google Patents

Description

The present invention relates to a fullerene derivative, a fullerene metal complex, and a production method thereof. Particularly, a derivative of fullerene C ₇₀ having a structure obtained by adding six organic groups C ₇₀ skeleton, fullerene C ₇₀ metal complex having a structure obtained by adding seven organic group C ₇₀ skeleton, and the C ₆₀ skeleton 8 The present invention relates to a fullerene C ₆₀ derivative having a structure to which a single organic group is added, and a method for producing them. In this specification, a fullerene derivative broadly means not only a molecule having a structure in which a specific group is added to fullerene but also a fullerene derivative including a fullerene metal complex in which a metal is coordinated to the molecule. And

Since large-scale synthesis method of fullerene C ₆₀ is established in 1990, studies on fullerene has been energetically developed. As a result, many fullerene derivatives have been synthesized and their various functions have been clarified. Along with this, various uses such as electron conductive materials, semiconductors, and physiologically active substances using fullerene derivatives have been developed (Non-Patent Documents 1 to 3).

The inventors of the present invention variously use fullerene compounds in which five organic groups are bonded to the skeleton of fullerene C ₆₀ (hereinafter referred to as “C ₆₀ skeleton” as appropriate) (hereinafter referred to as “5-addition C ₆₀ derivative”). It has been synthesized and reported (Patent Documents 1 to 3 and Non-Patent Documents 4 to 6). These five-added C ₆₀ derivatives have steric and electronic properties different from unsubstituted C _60, and thus are expected as new electron conductive materials, semiconductors, physiologically active substances, and the like.

In addition, as a derivative having a larger number of additional groups than a 5-addition C ₆₀ derivative, a fullerene compound in which 10 organic groups are bonded to the skeleton of fullerene C ₆₀ (hereinafter referred to as “10-addition C ₆₀ derivative” as appropriate) Are known (Patent Document 3 and Non-Patent Document 7), but fullerene compounds in which 8 organic groups are added to the C ₆₀ skeleton (hereinafter, referred to as “8-addition C ₆₀ derivatives” as appropriate) are known. Absent. In addition, in a conventionally known method for producing a 10-addition C ₆₀ derivative, after synthesizing a 5-addition C ₆₀ derivative, a hydrogen atom directly bonded to the C ₆₀ skeleton is converted into a cyano group, and further an organic group It is produced through a complicated multi-step process in which a 5-addition reaction is performed and a cyano group is finally removed.

On the other hand, the fullerene compound organic groups bonded to the fullerene C _70, 3 pieces of C ₇₀ derivatives organic group is bonded (hereinafter, appropriately referred to as "triple additional C ₇₀ derivatives".) It is known (Patent Documents 4 and Non-Patent Document 8). However, the fullerene C _70, 5-fold adduct similar to fullerene C _60, 6-fold adduct, 8 double adduct and 10 double adduct is not known, also, three organic groups are bonded Neither hexaadducts nor 7-polyadducts having two triple-addition sites are known.

Japanese Patent Laid-Open No. 10-167994 JP-A-11-255509 JP 2002-241323 A JP-A-11-255508 Hyundai Kagaku April 1992, page 12 Hyundai Chemistry June 2000, p. 46 Chemical Reviews, 1998, Vol. 98, p. 2527 Journal of the American Chemical Society, 1996, 118, p. 12850 Organic & Biomolecular Chemistry, 2003, Volume 1, p. 2604 Chemistry Letters, 2000, p. 1098 Journal of the American Chemical Society, 2003, 125, p. 2834 Journal of the American Chemical Society, 1998, 120, p. 8285

As described above, research on fullerene derivatives has been conducted so far. However still, the fullerene C ₆₀ and fullerene C _70, for example, an electronic material, a semiconductor, in order to provide useful materials as such as physiological active substances, it is desired to further develop a variety of derivatives.

The present invention has been made in view of the above problems, the fullerene such as C ₆₀ and C _70, and an object thereof is to provide novel derivatives and metal complexes, as well as a manufacturing method thereof.

The present inventors have to known fullerenes, were intensively studied to obtain a new derivative, by reacting the organocopper reagent fullerene C ₇₀ and C ₆₀ with monohydric, a new fullerene derivative sixfold It was found that an addition _C70 derivative and an 8-fold addition _C60 derivative can be obtained, and that a new fullerene metal complex can be obtained using these additions, and the present invention has been completed.

That is, the gist of the present invention, the fullerene C ₇₀ skeleton, wherein the organic group having 1 to 20 carbon atoms are bonded six resides fullerene derivative (claim 1).

Further, the fullerene derivative, the above C ₇₀ skeleton, the following partial structure (A), the partial structure (B), and a partial structure selected from the group consisting of partial structure (C), is assumed to be two chromatic .

｛上記の部分構造（Ａ）〜（Ｂ）において、Ｒはそれぞれ独立に、炭素数１〜２０の有機基を表わす。また、上記部分構造（Ｃ）において、Ｍは金属原子を表わし、ＬはＭの配位子を表わし、ｎは０以上の整数を表わす。｝
このとき、上記有機基は、置換基を有していても良い炭素数６〜２０の芳香族炭化水素基であることが好ましい（請求項２）。

{In said partial structure (A)-(B), R represents a C1-C20 organic group each independently. In the partial structure (C), M represents a metal atom, L represents a ligand of M, and n represents an integer of 0 or more. }
At this time, the organic group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent (claim 2).

Further, the fullerene derivative has a partial structure in which two partial structures selected from the group consisting of the partial structure (A), the partial structure (B), and the partial structure (C) are directly bonded to each other on the C ₇₀ skeleton. (Claim 3 ).

｛上記の部分構造（Ｆ）〜（Ｉ）において、Ｒ及びＲ’はそれぞれ独立に、炭素数１〜２０の有機基を表わし、Ｍ及びＭ’はそれぞれ独立に金属原子を表わし、Ｌ及びＬ’はそれぞれ独立にＭまたはＭ’はの配位子を表わし、ｎ及びｎ’はそれぞ独立に０以上の整数を表わす。｝ Another subject of the invention, the fullerene C ₇₀ is an organic group having 1 to 20 carbon atoms are bonded seven in the backbone, and characterized by having the above partial structure (C) 2 one on fullerene C ₇₀ skeleton to resides in fullerene metal complex (claim 4).
Furthermore, the fullerene C ₇₀ skeleton preferably has a partial structure selected from the group consisting of the following partial structure (F), partial structure (G), partial structure (H), and partial structure (I). (Claim 5).

{In the above partial structures (F) to (I), R and R 'each independently represent an organic group having 1 to 20 carbon atoms, M and M' each independently represent a metal atom, and L and L ''Independently represents M or M', and n and n 'each independently represents an integer of 0 or more. }

At this time, with respect to one fullerene C ₇₀ skeleton is preferable that two or three metal atoms is coordinated (claim 6).

Another gist of the present invention resides in a method for producing a fullerene derivative, comprising the step of reacting a fullerene with a monovalent organic copper reagent. (Claim 7 ).

The manufacturing method of the fullerene derivative is preferably carried out in the presence of a pyridine compound of the above reaction (claim 8).

  According to the present invention, a fullerene derivative can be obtained by reacting fullerene with a monovalent organocopper reagent, and another new fullerene derivative (fullerene metal) can be obtained using this fullerene derivative. Complex). These new fullerene derivatives are suitable for use in various fields such as electronic materials, semiconductors and physiologically active substances.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist thereof.

In the present invention, “fullerene” refers to a closed-shell carbon cluster formed by arranging carbon atoms in a spherical or rugby ball shape. The carbon number is usually 60 or more and 120 or less. Specific examples include C ₆₀ (so-called buckminster fullerene), C ₇₀ , C ₇₆ , C ₇₈ , C ₈₂ , C ₈₄ , C ₉₀ , C ₉₄ , C ₉₆ and higher order carbon clusters.
The present invention, in particular C ₆₀ and C ₇₀ of these fullerenes, as well as providing its derivatives and metal complexes, there is provided together these production methods.

In this specification, “fullerene derivative” means not only a compound having a structure in which a specific group is added to these fullerenes, but also a fullerene derivative including a fullerene metal complex in which a metal is coordinated to the molecule. Is meant broadly. Therefore, in this specification, the fullerene C ₇₀ derivative means a molecule having a structure in which 6 or 7 organic groups are added to the C ₇₀ skeleton (hereinafter referred to as “6-fold addition C ₇₀ derivative” and “7-fold respectively” respectively). additional C ₇₀ derivatives "hereinafter.), and, 6 polyaddition C ₇₀ derivatives or 7 polyaddition C ₇₀ fullerene metal complex metal is coordinated to derivative (hereinafter, as" 6 polyaddition C ₇₀ metal complexes, respectively, "and" 7 "Polyaddition _C70 metal complex"). Similarly, in the present specification, a fullerene C ₆₀ derivative refers to a molecule having a structure in which eight organic groups are added to the C ₆₀ skeleton (hereinafter referred to as “octaadded C ₆₀ derivative” as appropriate), and , And fullerene metal complexes in which a metal is coordinated to an 8-addition C ₆₀ derivative (hereinafter, referred to as “8-addition C ₆₀ metal complex” as appropriate).
The “skeleton” of fullerene refers to a carbon skeleton constituting a closed shell structure of fullerene or a fullerene derivative.

<1: 6 polyaddition fullerene C ₇₀ derivative>
First fullerene derivative of the present invention, fullerene C ₇₀ skeleton (hereinafter, as "C ₇₀ skeleton" that.) Is the 6 polyaddition C ₇₀ derivatives organic radicals R are bonded six to 20 carbon atoms . Hereinafter, the fullerene derivative appropriately referred to as "6 polyaddition C ₇₀ derivatives of the present invention".

The kind of the organic group R is not particularly limited as long as it is bonded to the C ₇₀ skeleton with a carbon atom, but usually an aromatic or aliphatic hydrocarbon group or heterocyclic group which may be substituted. It is. The carbon number of the organic group R is usually 1 or more, preferably 6 or more, and usually 20 or less. The organic groups R bonded to the same C ₇₀ skeleton may be the same or different.

Specific examples of the aromatic or aliphatic hydrocarbon group used as the organic group R include linear or branched chain alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group; a cyclopropyl group and a cyclopentyl group Cyclic alkyl groups such as cyclohexyl group; linear or branched chain alkenyl groups such as vinyl group, propenyl group, hexenyl group; cyclic alkenyl groups such as cyclopentenyl group, cyclohexenyl group; ethynyl group, 1-propionyl group, etc. Alkynyl groups; aryl groups such as phenyl groups, biphenyl groups, toluyl groups, and naphthyl groups; aralkyl groups such as benzyl groups and phenethyl groups. Among these specific examples, from the viewpoint of stability and ease of handling of the C ₇₀ derivative, a phenyl group, an aryl group such as a naphthyl group (aromatic hydrocarbon group) are preferred, phenyl group is particularly preferred. In addition, examples of the heterocyclic group include a 2-thienyl group, a 2-pyridyl group, a furfuryl group, and the like.

  When the aromatic or aliphatic hydrocarbon group used as the organic group R has a substituent, the type of the substituent is not particularly limited unless it is contrary to the gist of the present invention. Examples of substituents include: alkyl groups such as methyl, ethyl and butyl groups; aryl groups such as phenyl and naphthyl groups; alkoxy groups such as methoxy and ethoxy groups; aryloxy groups such as phenoxy groups; tertiary Amino group; halogen atom such as fluorine atom; silyl group such as trimethylsilyl group and triethoxysilyl group; hydroxy group; thiol group; alkylthio group such as butylthio group; arylthio group such as phenylthio group; acyl group such as acetyl group; And carbonyloxy group such as a group. Among them, since the reaction with the Grignard reagent may be performed in one step, an alkyl group such as a methyl group, an ethyl group or a butyl group; an aryl group such as a phenyl group or a naphthyl group; an alkoxy group such as a methoxy group or an ethoxy group; An aryloxy group such as a phenoxy group; a tertiary amino group; a fluorine atom and a chlorine atom among halogen atoms; a silyl group such as a trimethylsilyl group and a triethoxysilyl group; an alkylthio group such as a butylthio group; and an arylthio group such as a phenylthio group In particular, an alkyl group, an aryl group, an alkoxy group, and a chlorine atom are more preferable. In addition, when an aromatic or aliphatic hydrocarbon group has a substituent, the total carbon number of the organic group R including the carbon number of the substituent needs to exist in the said range.

Throughout this specification, all organic groups represented by “R” shall have the same definition as described above. In addition, for convenience of explanation, “R ′” may be used to represent an organic group, but the organic group represented by “R ′” is the same as “R” described above unless otherwise specified. Represents the definition of. In addition, when a plurality of organic groups R and / or R ′ are bonded to the same fullerene C ₆₀ skeleton or C ₇₀ skeleton, these organic groups R and / or R ′ are respectively unless otherwise specified. It may be the same or different.

The relative bonding position of the six organic groups R with respect to the C ₇₀ skeleton is not particularly limited, and may be bonded to an arbitrary position. However, in the production of 6 polyaddition C ₇₀ derivatives of the present invention by a manufacturing method described below (production method of the present invention), a known method (see Patent Document 4 and Non-Patent Document 8) C ₇₀ 3 As in the case of adding one organic group R, usually, a portion in which three organic groups R and one hydrogen atom are added to the C ₇₀ skeleton at relative positions represented by the following formulas (A) and (B) Those having a structure (hereinafter, appropriately referred to as “triple-added partial structure (A)” and “triple-added partial structure (B)”) are obtained. For this reason, from the viewpoint of ease of production, the hexaaddition _C70 derivative of the present invention is a hexaaddition in which a total of two triple addition partial structures (A) and (B) below are present on the _C70 skeleton. Addition _C70 dihydro derivatives are preferred. In the following triple addition partial structures (A) and (B), R independently represents the above-described organic group.

Here, the triple addition partial structure (A) and the triple addition partial structure (B) are in an enantiomeric relationship with each other. The hexaaddition _C70 derivative of this invention should just have one or both among said triple addition partial structure (A) and triple addition partial structure (B). That is, only one triple addition partial structure may be provided on the C ₇₀ skeleton, or both triple addition partial structures may be provided on the C ₇₀ skeleton.

In particular, when the hexaaddition _C70 derivative of the present invention is produced by the production method described later (the production method of the present invention), the triple addition partial structure (A) and / or the triple addition partial structure (B) is selected. part 3 polyaddition partial structure selected is bonded to two direct structure (hereinafter. referred to as "6 polyaddition partial structure") 6 polyaddition C _70-dihydro derivatives having, particularly, the following 6 polyaddition Among the six types of 6-added _C70 dihydro derivatives each having the partial structures (I) to (VI), any one is obtained alone or two or more are obtained as a mixture. Thus, the 6 polyaddition C ₇₀ derivatives of the present invention, in particular, 6 polyaddition C _70-dihydro derivatives having any of the following 6 polyaddition partial structure (I) ~ (VI) are preferred. In the following six-addition partial structures (I) to (VI), each R independently represents the organic group described above.

That is, the sextuple The additional C _70-dihydro derivatives, C ₇₀ 3 kinds of position isomers exist based on the difference in position of direct the hydrogen atoms attached to the backbone, yet two types of mirror image to each regioisomer Isomers {ie, pairs of 6-addition substructure (I) and 6-addition substructure (II); 6-addition substructure (III) and 6-addition substructure (IV); 6-addition Since there are pairs of partial structure (V) and hexaaddition partial structure (VI)}, there are 6 types of isomers in 3 × 2. All of these six isomers correspond to the hexaaddition _C70 derivative of the present invention. In addition, any two or more of these six isomers, and even a mixture of all six isomers, are included in the hexaaddition _C70 derivative of the present invention.

In the triple addition partial structures (A) and (B), all of the sp ² carbons other than the four carbons to which the organic group R or hydrogen atom is bonded are conjugated. Therefore, in the 6 polyaddition C ₇₀ derivatives of the present invention, a 70-4-4 = 62π-electron conjugated of.

Since the hexaaddition _C70 derivative of the present invention has six organic groups R in one _C70 skeleton, aromatic hydrocarbons such as toluene and xylene, and ester organics may be used depending on the type of the organic group R. solubility in a solvent, such as solvent, is expected to be higher than that fullerene C ₇₀ itself or known triple additional C ₇₀ derivatives. High solubility in a solvent is advantageous when the C ₇₀ derivative is dissolved in a solvent as in coating or when a reaction is carried out with respect to the C ₇₀ derivative.

Furthermore, depending on the type of the organic group R, it is possible to extract a hydrogen atom on the C ₇₀ skeleton using a base to form an anion. In this case, the 6-addition _C70 derivative of the present invention is a bifunctional C ₇₀ that can be synthesized by raw materials of fullerene metal complexes described in the following <3: Fullerene metal complexes> or by alkylation of anion sites. It is useful and preferable as a raw material for ₇₀ derivatives.

In particular 6 polyaddition C _70-dihydro derivatives described above, C ₇₀ relative binding positions of the six organic groups R and two hydrogen atoms have been identified on skeletal, that there is regularity in its structure Therefore, it is useful as an electronic material, a physiologically active substance, a structural unit for forming a nanostructure, or a raw material thereof.

<2: 8 polyaddition fullerene C ₆₀ derivative>
The second fullerene derivative of the present invention is a 8 polyaddition C ₆₀ derivatives organic radicals R are bonded eight backbone carbons 1 to 20 of fullerene C _60. Hereinafter, this fullerene derivative is referred to as “an 8-addition C ₆₀ derivative of the present invention” as appropriate.

In the C ₆₀ skeleton, the position at which the organic group R is bonded is not particularly limited, as long as it is bonded to an arbitrary position. However, according to the production method described later, the 8-addition C ₆₀ derivative of the present invention usually has one of the above-mentioned triple addition partial structure (A) or triple addition partial structure (B) on the C ₆₀ skeleton. And an 8-fold addition C ₆₀ dihydro derivative having one partial structure (D) (D), to which five organic groups R are added (hereinafter referred to as “5-fold addition partial structure” as appropriate) on the C ₆₀ skeleton. can get.

In particular, when the 8-addition C ₆₀ derivative of the present invention is produced by the production method described later (the production method of the present invention), the above-described triple-addition partial structure (A) or triple-addition partial structure (B) and the above-mentioned 5-addition C ₆₀ derivative (8-addition C ₆₀ dihydro derivative) having a partial structure (hereinafter appropriately referred to as “8-addition partial structure”) directly bonded to the partial structure (D), for example, the following structural diagram (1 ) 8 polyaddition C _60-dihydro derivative represented to obtain.

Specifically, one kind of simple substance or a mixture of two or more kinds among ten kinds of eight-addition C ₆₀ dihydro derivatives having the following eight-addition partial structures (i) to (x) are obtained. Although what kind of isomers and a mixture are obtained varies depending on the reaction conditions, a mixture of all these 10 isomers is usually obtained.

That is, in the 8-addition partial structure, there are five hydrogen atom bonding positions in the 5-addition partial structure (D), and the hydrogen atom bonding positions in the triple-addition partial structure are triple-addition partial structures ( since there are two types of a) or triple additional partial structure (B), 8 polyaddition C ₆₀ 5 × 2 = 10 kinds of isomers as dihydro derivative (5 regioisomers × respective two mirror image Isomer) will be present. All of these 10 isomers correspond to the 8-addition C ₆₀ derivative of the present invention. In addition, a mixture of any two or more of these 10 isomers, and a mixture of all 10 isomers are also included in the 8-addition C ₆₀ derivative of the present invention.

As described above, in the triple addition partial structures (A) and (B), all the sp ² carbons other than the four carbons to which the organic group R or hydrogen atom is bonded are conjugated. Further, in the 5-addition partial structure (D), the cyclopentadiene moiety is separated from the conjugation by the carbon to which the organic group R is bonded, and the remaining carbon is conjugated. Therefore, in the 8-addition C ₆₀ derivative of the present invention, it becomes a conjugate of 60-4-10 = 46π electron system.

8 polyaddition C ₆₀ derivatives of the present invention is a derivative of fullerene C ₆₀ having a specific structure, an electronic material, a physiologically active substance, a structural unit of the nanostructure formation, or are useful as raw materials thereof. In particular, unlike a 10-added C ₆₀ derivative, it has an asymmetric structure and is expected to have a unique electronic state.

In particular, in the case of the above-mentioned 8-addition C ₆₀ dihydro derivative, the relative bonding positions of the eight organic groups R with respect to the C ₆₀ skeleton are specified, and the structure is regular. It is useful as an electronic material, a physiologically active substance, a structural unit for forming a nanostructure, or a raw material thereof.

<3: Fullerene metal complex>
6 polyaddition C ₇₀ derivatives and 8 polyaddition C ₆₀ derivatives of the present invention, in particular 6 polyaddition C _70-dihydro derivatives and 8 polyaddition C _60-dihydro derivatives, a hydrogen atom directly bonded to the fullerene skeleton metal atom or metal-containing group To obtain a metal complex having a fullerene skeleton (hereinafter, this metal complex is referred to as “the fullerene metal complex of the present invention” as appropriate). These fullerene metal complexes of the present invention are also included in the fullerene derivative of the present invention. As the fullerene metal complexes of the present invention, the metal complex is synthesized using 6 polyaddition C _70-dihydro derivative (hereinafter appropriately abbreviated as "6 polyaddition C ₇₀ metal complex."), The 6 polyaddition C ₇₀ metal complex derived from a metal complex (hereinafter appropriately abbreviated as "7 polyaddition C ₇₀ metal complex."), as well as 8 polyaddition C ₆₀ metal complexes which are synthesized using the dihydro derivative (hereinafter to as "8-fold Abbreviated as "addition _C60 metal complex").

6 polyaddition C ₇₀ metal complex of the present invention, in the structure of 6 polyaddition C _70-dihydro derivatives of the above, by at least one metal atom or metal-containing group of two hydrogen atoms bonded directly to C ₇₀ backbone It has a substituted structure. Specifically, it has two partial structures (hereinafter referred to as “triaddition metal complex partial structure”) (C) as appropriate on the C ₇₀ skeleton, or the above triple addition partial structure (A ) Or one triple addition partial structure (B) and one triple addition metal complex partial structure (C).

6 polyaddition C ₇₀ metal complex of the present invention, as described above, by replacing hydrogen atoms bonded directly to C ₇₀ backbone of 6 polyaddition C ₇₀ derivatives, is easily synthesized. Therefore, from the viewpoint of ease of production, the hexaaddition _C70 metal complex of the present invention includes partial structures corresponding to the above-described hexaaddition partial structures (I) to (VI) of the hexaaddition _C70 derivative, That is, a partial structure in which two triple addition metal complex partial structures (C) are directly bonded, and the triple addition metal complex partial structure (C) and the triple addition partial structure (A) or (B). DOO any of the partial structure of the bound moiety directly (hereinafter, appropriately referred to as "6 polyaddition C ₇₀ metal complex partial structure".) preferably 6 polyaddition C ₇₀ metal complex having. Specifically, 6 polyaddition C ₇₀ metal complex having the following 6 polyaddition C ₇₀ metal complex partial structure (VII) ~ (XII) are preferred.

Here, these 6-addition _C70 metal complex partial structures (VII) and (VIII) pairs, 6-addition _C70 metal complex partial structures (IX) and (X) pairs, 6-addition _C70 metal complexes partial structure (XI), the relationship of each pair are enantiomers each other (XII) but, C ₇₀ metal complex having either enantiomer structures, corresponding to 6 polyaddition C ₇₀ metal complex of the present invention. Also, mixtures of 6 polyaddition C ₇₀ metal complex having these 6 polyaddition C ₇₀ metal complex partial structure (VII) ~ (XII), are intended to be included in the 6 polyaddition C ₇₀ metal complex of the present invention.

In the above hexaaddition _C70 metal complex partial structures (VII) to (XII), M represents a metal atom. There is no particular limitation on the type of metal atom M, and any metal atom can be used. However, a metal selected from a typical element of Group 1 to Group 10 and a transition metal element is desirable. Specific examples include Li, Na, K, Cs, Tl, Mo, W, Re, Fe, Ru, Rh, Ir, and Pd. Particularly preferred are Group 1 metal atoms and Group 8 transition metals. Group 1 metal complexes are useful as reactive intermediates because of their reactivity at the cyclopentadienyl site of the fullerene skeleton, while group 8 transition metal complexes are stable and can be used as various materials as they are. Or it is useful as a raw material of the 7 addition _C70 metal complex of the present invention mentioned below, and is preferred respectively.

  Further, L represents a ligand of a metal atom M. The ligand L is not particularly limited as long as it corresponds to the type and valence of the metal atom M, and specifically, a π-coordinated configuration such as olefin, CO or tertiary phosphine. Examples thereof include ligands and ligands bonded by σ bonds such as halogen, alkoxy, alkyl, and hydrogen. Examples of L include solvent molecules that can coordinate with unpaired electrons, such as tetrahydrofuran and diethyl ether.

The ligand L in the case where the metal atom M is a Group 1 metal (alkali metal) is usually a solvent molecule having coordination properties, and is a solvent used during synthesis or purification. Among these, a strongly coordinated solvent such as tetrahydrofuran is preferable because it has an effect on stabilization of the complex. Further, when the metal atom M is a group 8 transition metal, the ligand L is preferably a multidentate ligand that forms a stable complex, and more preferably an η ⁵ coordination type ligand. Specifically, an optionally substituted cyclopentadienyl group is most preferable. Depending on the type of metal atom M, the ligand L is not always necessary.

  N represents the number of ligands L. n is an integer of 0 or more, and is usually 0-3. In addition, when n is 2 or more, each ligand L may be the same or different.

Throughout this specification, the metal atom represented by “M”, the ligand represented by “L”, and the number represented by “n” all represent the same definition as described above. . For convenience of explanation, a metal atom represented by “M ′”, a ligand represented by “L ′”, and “n ′” may be used, but these “M ′”, “L” The numbers represented by “” and “n ′” also represent the same definitions as “M”, “L”, and “n” described above unless otherwise specified. When a plurality of “ML _n ” and / or “M′L ′ _{n ′} ” are bonded to the same fullerene C ₆₀ skeleton or C ₇₀ skeleton, these “ML _n ” and / or “M′L” '_n'' may be the same or different unless otherwise specified.

As described above, when the hexaaddition C ₇₀ metal complex of the present invention has two triple addition metal complex partial structures (C), the two ML _n possessed by the hexaaddition C ₇₀ metal complex are: , May be of the same kind or different.

In the case of having two triple addition metal complex partial structures (C), the hexaaddition C ₇₀ metal complex of the present invention has a structure having two metal atoms M in one C ₇₀ skeleton. A continuous structure can be formed by selecting the polyvalent metal atom M. Here, for example, as shown in the following chemical formula, the continuous structure means that a single metal atom M is shared between two hexaaddition _C70 metal complexes, thereby a plurality of hexaaddition _C70. A structure in which metal complexes are connected to each other.

このように連続的な構造を形成することができるため、本発明の６重付加Ｃ₇₀金属錯体はナノ構造形成の構造単位として有用である。

Thus, since a continuous structure can be formed, the hexaaddition _C70 metal complex of this invention is useful as a structural unit of nanostructure formation.

Further, if the type of metal atom M is appropriate, two metal atoms M can exist relatively close to each other. Therefore, the six-addition _C70 metal catalyst of the present invention involves the two metal atoms M. It is expected to show catalytic activity in specific catalytic reactions.

On the other hand, 8 polyaddition C ₆₀ metal complex of the present invention, in the structure of the 8 polyaddition C _60-dihydro derivatives of the foregoing, like the above-described 6 polyaddition C ₇₀ metal complexes, two attached directly to C ₆₀ backbone It has a structure in which at least one of the hydrogen atoms is replaced by a metal atom or a metal-containing group. Specifically, on the C ₆₀ skeleton, the above-described triple addition metal complex partial structure (C) and the following partial structure (hereinafter, referred to as “penta addition metal complex partial structure” as appropriate) (E): It has one or both of them.

As described above, the octaaddition C ₆₀ metal complex of the present invention can be easily obtained by substituting the hydrogen atom directly bonded to the C ₆₀ skeleton of the octaaddition C ₆₀ derivative, as in the case of the hexaaddition C ₇₀ derivative. Synthesized. Therefore, from the viewpoint of ease of production, the octaaddition C ₆₀ metal complex of the present invention includes partial structures corresponding to the above-described octaaddition partial structures (i) to (x) of the 8-addition C ₆₀ derivative, That is, the partial structure in which the triple addition metal complex partial structure (C) and the pentaaddition metal complex partial structure (E) are combined, the triple addition metal complex partial structure (C), and the pentaaddition partial structure (D). A partial structure in which 3 is added, a partial structure in which a triple addition partial structure (A) and a pentaaddition metal complex partial structure (E) are combined, and a triple addition partial structure (B) and a pentaaddition metal complex partial structure An 8-fold addition C ₆₀ metal complex having a partial structure selected from the group consisting of a partial structure bonded with (E) (hereinafter referred to as “8-addition C ₆₀ metal complex partial structure” as appropriate) is preferred. Specifically, 8 polyaddition C ₆₀ metal complex having the following 8 polyaddition C ₆₀ metal complex moiety (xi) ~ (xviii) are preferred.

Here, among the double-added C ₆₀ metal complex partial structures, the pair (xii) and (xiii), the pair (xv) and (xviii), and the pair (xvi) and (xvii) are enantiomerically related to each other. Although, even C ₆₀ metal complex having either enantiomer structure, corresponding to 8 polyaddition C ₆₀ metal complex of the present invention. Mixture of 8 polyaddition C ₆₀ metal complex having 8 polyaddition C ₆₀ metal complex partial structure (xi) ~ (xviii) should also be included in the 8 polyaddition C ₆₀ metal complex of the present invention.

In addition, when the octaaddition _C60 metal complex of this invention has both a triple addition metal complex partial structure (C) and a pentaaddition metal complex partial structure (E), the octaaddition _{C60 is shown.} The two ML _n possessed by the metal complex may be the same or different.

Also, if having a triple additional metal complex partial structure (C) and 5 polyaddition metal complex moiety (E), 8 polyaddition C ₆₀ metal complex of the present invention, 6 polyaddition C ₇₀ metal complex of the present invention In the same manner as above, it is possible to form a continuous structure, which is useful as a structural unit for nanostructure formation. If the type of metal atom M is appropriate, it can be used for a specific catalytic reaction involving metal atom M. It is expected to show activity as a catalyst.

<4: 7-addition _C70 metal complex>
Next, the 7-addition _C70 metal complex which is another gist of the present invention will be described. 7 polyaddition C ₇₀ metal complex of the present invention is a metal complex of 7 polyaddition C ₇₀ derivatives organic group having 1 to 20 carbon atoms is bonded seven skeleton of the fullerene C _70. Hereinafter, this fullerene derivative is appropriately referred to as “the seven-addition C ₇₀ metal complex of the present invention”.

Examples of the organic groups bonded to the C ₇₀ skeleton, the above <1: 6 polyaddition fullerene C ₇₀ derivative> are the same as those described organic groups R described in the column also bind to C ₇₀ backbone the metal ligands, described above: are the same as those of the ligand ML _n described in the section of <3 fullerene metal complexes>. Here, R, M, L, n definitions above <1: 6 polyaddition fullerene C ₇₀ derivatives> and: is as described in the section of <3 fullerene metal complexes>. The number of metal atoms bonded to one C ₇₀ skeleton is not particularly limited, but the metal is easily produced by the production method described in the following section <7: Reaction of introducing alkyl group into fullerene metal complex>. Those in which two or three atoms are bonded are preferred.

In the _C70 skeleton, the position where the organic group R and the metal atom M are bonded is not particularly limited as long as it is bonded to an arbitrary position. However, below: According to the manufacturing method described in the section of <7 alkyl group introduction reaction into the fullerene metal complexes> 7 polyaddition C ₇₀ metal complex of the present invention, C ₇₀ the following partial structure (C) A C ₇₀ derivative having two on the skeleton and further having one organic group R ′ at an arbitrary position on the C ₇₀ skeleton is preferable.

In this case, one bond is left, but a hydrogen atom is bonded or a metal atom (hereinafter, this is represented by M ′. The ligand is L ′, and the number of ligands is n. '). The former is a binuclear complex in which two metal atoms are bonded to one fullerene skeleton. Its molecular formula is (C ₇₀ R ₆ R ′) (ML _n ) ₂ H, and the latter has three metal atoms bonded to the fullerene skeleton. The molecular formula thereof is (C ₇₀ R ₆ R ′) (ML _n ) ₂ (M′L ′ _{n ′} ).

Among these, particularly preferred 7-addition _C70 metal complexes are either one of the following partial structures (F) and (G) in a binuclear complex, and the following partial structures (H) and (I) in a trinuclear complex. Those having any one of these are mentioned. These six polyaddition C ₇₀ metal complex of the present invention described above as a raw material, described below <7. This is preferable because it can be easily synthesized by the production method described in the column of introduction reaction of alkyl group to fullerene metal complex>.

The seven-addition _C70 metal complex of the present invention has not been reported so far, and is a unique compound in which metal atoms are coordinated at high density on fullerene. Useful. In addition, since bonds can be extended from one fullerene center in two or three directions via a metal atom, it is also useful as an element for constructing a molecular-sized nanostructure. In addition, if the types of metal atoms M and M ′ are appropriate, it is expected to exhibit activity as a catalyst in a specific catalytic reaction involving the metal atom M.

<5: Production method of fullerene derivative>
As a method for producing a fullerene derivative of the present invention (6 polyaddition C ₇₀ derivatives and 8 polyaddition C ₆₀ derivatives) is not particularly limited, for example, fullerene C ₇₀ or fullerene C _60, monovalent The method of making it react with an organic copper reagent is mentioned. Hereinafter, these production methods (hereinafter, respectively appropriately referred to as "production method of C ₇₀ derivatives of the present invention", "method for manufacturing a C ₆₀ derivative of the present invention".) Will be described in detail.

As the fullerene C _70, C ₆₀ of the raw material, it is possible to use those which are synthesized by various known methods. As a synthesis method of fullerene, for example, Nature, 1990, 347, p. 354, a method of arc discharge of graphite, Nature, 1991, Vol. 352, p. 139 to incompletely burn the organic matter. Fullerenes are usually contained in soot obtained by these methods, and are extracted with an organic solvent such as benzene or toluene to obtain a plurality of fullerenes having different carbon numbers as a mixture. As the raw material of the production method of the present invention, the mixture to the may be subjected to separation and purification from a single piece of C _70, C _60, etc. to the following manufacturing method, subjected to leave the following manufacturing method of the mixture, resulting The target _C70 derivative and _C60 derivative may be obtained by separating and purifying the obtained mixture of fullerene derivatives and the like.

[5-1: 6 polyaddition method for producing C ₇₀ derivatives]
The C ₇₀ derivative production method of the present invention, the fullerene C ₇₀ of the raw material is reacted with an organocopper reagent monovalent. Usually, this reaction is carried out in an appropriate solvent system. The type of the solvent system is not particularly limited, but it is preferable that pyridines are present.

(Raw materials and reagents)
Fullerene C ₇₀ of the raw material, although it may be used those obtained by the method described above, usually used after a state of solution or slurry with the organic solvent. As the organic solvent, usually, the solubility is relatively high aromatic hydrocarbons or halogenated aromatic hydrocarbons of fullerene C ₇₀ is used. Specific examples include toluene, xylene, ethylbenzene, butylbenzene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, dimethylnaphthalene, diisopropylnaphthalene and the like. In addition, these organic solvents may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. The amount of organic solvent is usually 100mL or more with respect to fullerene C ₇₀ of 1g, which is the range of normal 10L.

In the case where pyridines described later are used in the reaction system, if the pyridines used are liquid at room temperature, the fullerene C ₇₀ is dissolved or slurried using the pyridines instead of the organic solvent exemplified above. It can also be made.

The monovalent organic copper reagent is represented by the general formula RCu. Wherein the organic group R, the above <1: 6 polyaddition fullerene C ₇₀ derivative> has the same meaning as the organic group R described in the column of, usually intact, sextuple of the present invention is the reaction product It is introduced onto the C ₇₀ skeleton as an organic group R in the addition C ₇₀ derivative. In particular, when an aromatic hydrocarbon group such as a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group is used as the organic group R, the organic copper reagent RCu has appropriate reactivity and stability. Particularly preferred. In addition, a monovalent organic copper reagent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The method for synthesizing the monovalent organic copper reagent is not particularly limited, and any synthesis method can be used. Particularly preferred methods include a method of synthesizing from a Grignard reagent and a monovalent copper reagent. Here, each of the Grignard reagent and the monovalent copper reagent may be used alone, or two or more kinds thereof may be used in combination in any ratio and combination.

  The Grignard reagent is a reagent represented by the general formula RMgX. Here, X represents a halogen atom of Cl, Br, or I, and the organic group R has the same meaning as R in the above-mentioned organic copper reagent RCu. The Grignard reagent is usually used in the form of a solution of an ether solvent such as diethyl ether or tetrahydrofuran (THF). The concentration varies depending on the type of the organic group R and the halogen atom X, but is usually from 0.1M to 2.0M.

Monovalent copper reagents are usually used in the form of halides. Specifically, CuCl, CuBr, CuI, etc. are illustrated. In order to carry out the reaction with good reproducibility, it is not preferable to use commercially available products of these halides as they are. For the purpose of removing impurities, especially zero-valent or divalent copper compounds, it is preferable to use those purified by a technique such as recrystallization. Most preferred is a CuBr · Me ₂ S complex having Me ₂ S purified by crystallizing CuBr from Me ₂ S as a crystal solvent. Here, “Me” represents a methyl group.

  Pyridines refer to any substance having a pyridine skeleton in the molecular structure. Examples thereof include pyridine, methylpyridines, ethylpyridines, dimethylpyridines, chloropyridines, aminopyridines, quinoline, isoquinoline, methylquinolines, etc. Among them, pyridine, methylpyridines, ethylpyridine And those having a monocyclic pyridine skeleton such as dimethylpyridines, chloropyridines and aminopyridines. In addition, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and ratios.

The effect of pyridines on the reaction of adding organic group R to fullerene C ₇₀ is not clear, but pyridines are known to have a strong interaction with fullerene, and also have an interaction with organocopper reagent RCu. since it is believed that, as compared with the case of performing the reaction without using pyridines, pyridines acts on one or both of the fullerene C ₇₀ or organocopper reagent RCu, changes reactive This is probably because of this.

(Reaction procedure and reaction conditions)
Reaction of the organic copper reagent fullerene C ₇₀ with monohydric, compared organocopper reagent resulting monovalent and a Grignard reagent with a monovalent copper reagent, preferably in the presence of pyridine, reacting fullerene C ₇₀ It is carried out by letting.

The order of mixing the raw material fullerene C ₇₀ , the Grignard reagent, and the copper reagent is not particularly limited, and an organic copper reagent obtained from the Grignard reagent and the copper reagent and fullerene C ₇₀ can be reacted. Can be mixed in any order. For example, first, by reacting a Grignard reagent and a copper reagent organocopper reagent prepared (organocopper reagent preparation reaction), followed by which the addition of fullerene C ₇₀ is added to an organic group with (an organic radical additions to the fullerene C ₇₀ (Reaction) may be performed in a two-step process. Further, coexist fullerene C ₇₀ in the synthesis of the organic copper reagent RCu from copper reagent and the Grignard reagent RMgX, performed an organic group addition reaction to an organocopper reagent prepared reacting a fullerene C ₇₀ in a one-step process Also good. The following convenience of description, as an example a case in which divided the organic group addition reaction to an organocopper reagent prepared reacting a fullerene C ₇₀ in two steps, will be described reaction conditions of each step, one step process The reaction conditions are basically the same in the case where the reaction is carried out.

(Organic copper reagent preparation reaction)
In the preparation reaction of the organic copper reagent, the usage ratio of the Grignard reagent and the copper reagent is usually 1.0 equivalent or more and 1.5 equivalent or less of the copper reagent with respect to the Grignard reagent. If the amount of the Grignard reagent to copper reagent is in excess, unfavorable not obtained reproducibility of the reaction between the organic copper reagent and fullerene C ₇₀ obtained. However, when two or more types of Grignard reagent or copper reagent are used, the total amount used is within the above range. The amount of concentration and pyridines of the Grignard reagent used, when the organic group addition reaction to the fullerene C _70, organocopper reagent concentration in the reaction solution with fullerene C ₇₀ and organocopper reagent is determined.

  The reaction temperature during the preparation reaction of the organocopper reagent depends on the type of Grignard reagent and monovalent copper reagent used. For example, when the preparation reaction is carried out in one step, it is usually from -78 ° C to 50 ° C. Yes, preferably about room temperature. The reaction time is usually about several minutes to 1 hour.

(Organic group addition reaction to the fullerene C ₇₀₎
Using the ratio of the organic copper reagent and fullerene C ₇₀ in the organic group addition reaction to the fullerene C ₇₀ is, RCu: in the molar ratio of C _70, usually 6: 1 or more, preferably 9: 1 or more, and usually 200 : 1 or less, preferably 100: 1 or less. When a plurality of types of organic copper reagents are used, the total is set within the above molar ratio range.

The reaction temperature for the organic group addition reaction to the fullerene C ₇₀ is usually -78 ° C. or higher, preferably at 0 ℃ or higher, and usually 50 ° C. or less, preferably 40 ° C. or less, more preferably about room temperature. The reaction time is usually from 10 minutes to several days.

(Use of pyridines)
When using a pyridine, time adding pyridine to the reaction system is arbitrary, if it is possible to advance the reaction between the organic copper reagent and fullerene C ₇₀ in the presence of a pyridine compound, is not otherwise limited. For example, it may be allowed to coexist in the reaction system from the time of adjusting the reaction of the organic copper reagent, in addition later to produce organic copper reagents may perform organic group addition reaction to the fullerene C _70. Furthermore, it may be used as a solvent for dissolving or slurrying the fullerene C ₇₀ as described above.

The amount of pyridine used is generally 10% or more, preferably 20% or more, and usually 90% or less, in a volume ratio with respect to the total amount of solvent (total amount of the organic copper reagent solution, pyridines and organic solvent). The range is preferably 80% or less. When pyridines is too small, even by reacting a large excess of the organic copper reagent RCu, only 3 polyaddition C ₇₀ derivatives such as disclosed in Patent Document 4 and Non-Patent Document 8 is obtained, the objective 6 polyaddition C ₇₀ derivatives have been no possibility that obtained.

(Stop reaction)
The addition reaction of the organic group R can be stopped by mixing an acid such as an aqueous HCl solution. Usually, an HCl aqueous solution of 1 wt% or more and 10 wt% or less is added in excess to the organocopper reagent RCu.

After stopping the reaction, the reaction solution is dried with anhydrous magnesium sulfate or anhydrous sodium sulfate, and then passed through a column of celite, silica gel, alumina, etc., and by-produced Cu salt, Mg salt or dried by addition reaction. Remove agents. Thereafter, the reaction liquid is concentrated to about 1/3 to 1/50, and a poor solvent such as CH ₃ OH and CH ₃ CH ₂ OH is added to the concentrated reaction liquid 10 to 1000 times to achieve the target. obtain the crude product of C ₇₀ derivatives. And here poor solvent means a solubility of 6 polyaddition C ₇₀ derivatives of the present invention is a low solvent, usually, the solubility of 6 polyaddition C ₇₀ derivatives of the present invention refers to the following 1 mg / L.

(C ₇₀ derivative obtained by reaction)
The yield of the desired product (6 polyaddition C ₇₀ derivatives of the present invention) may vary depending on the type and the reaction conditions of the organic radical R to be introduced, normally, as a value in terms of pure product of the object, generally 30% or more, 90% or less. Further, the purity of the target compound in the crude product described above (6 polyaddition C ₇₀ derivatives of the present invention), as an analytical value of HPLC (high performance liquid chromatography), usually 60% or more, with a purity degree of 95% or less can get. If necessary, further purification can be performed by a usual method such as column chromatography or HPLC. Moreover, the above-mentioned three kinds of positional isomers can also be separated by these methods.

The obtained product is identified as the target product (hexaadded _C70 derivative of the present invention) by, for example, ¹ H-NMR, ¹³ C-NMR and MS analysis, but also by X-ray crystal diffraction. Can be confirmed. Furthermore, only one enantiomer of 6 polyaddition C ₇₀ derivatives of the present invention obtained, such as HPLC using a chiral column, divided by the conventional optical resolution techniques, can be isolated.

As described above, the 6-addition _C70 dihydro derivative of the present invention includes 6 types of isomers (3 types of positional isomers × 2 types) each having the above 6-addition partial structures (I) to (VI). Enantiomers of According to the production method of the present invention, any one of these six types of isomers or a mixture of two or more types can be obtained. Although what kind of isomers and a mixture are obtained varies depending on the reaction conditions, a mixture of all these six isomers is usually obtained. In particular, when a substantially chiral component is not contained in the reagent or solvent used in the production, and further other additives, any C ₇₀ derivative having an enantiomer relationship in each positional isomer is 1: It produces | generates by the ratio of 1, and what is called a racemate is obtained. In this case, in ¹ H-NMR analysis, the hydrogen atom directly bonded to the C ₇₀ skeleton is composed of two singlet peaks based on equivalent hydrogen atoms corresponding to two types of C ₂ symmetric isomers. A total of four singlet peaks appearing with two equal intensity singlet peaks corresponding to two non-equivalent hydrogen atoms of the C ₁ symmetric isomer, and the peaks do not overlap each other Are observed as four singlet peaks.

6 polyaddition C ₇₀ derivative obtained by the production method of 6 polyaddition C ₇₀ derivatives of the present invention is a C ₇₀ derivative six organic groups R and two hydrogen atoms on the particular relative positions added, electrons It is useful as a material, a physiologically active substance, a structural unit for forming a nanostructure, and a raw material thereof.

(Other)
Note that the 6 polyaddition method for producing C ₇₀ derivatives of the present invention, when applied in triplicate additional C ₇₀ derivative described in Patent Document 4 and Non Patent Document 8, i.e., a monovalent triplicate additional C ₇₀ derivatives Even when the organic copper reagent RCu is reacted, the 6-addition _C70 derivative of the present invention having 6 organic groups R bonded thereto can be produced. This case, it is possible to the material of the organic group (3 polyaddition C ₇₀ organic group derivative has) and newly introduced organic group (organic group to be introduced by an organic copper reagent RCu) different, this method Therefore, a _hexaaddition C70 derivative having a triple addition partial structure (triaddition site) of two different organic groups can also be produced.

[5-2: Method for producing octaaddition C ₆₀ derivative]
8 duplex method for producing additional C ₆₀ derivatives of the present invention includes a method for producing a 6 polyaddition C ₇₀ derivatives of the present invention described above is basically the same. Specifically, fullerene C ₆₀ may be used instead of fullerene C ₇₀ as a raw material. Other synthetic methods and reaction conditions are the same as in the method for producing the hexaadded _C70 derivative of the present invention.

As described above, the octaaddition C ₆₀ dihydro derivative of the present invention has 10 types of isomers (5 types of positional isomers × 2 types) each having the above-described 8-addition partial structures (i) to (x). The enantiomers of In the production method of the present invention, any one of these 10 kinds of isomers or a mixture of 2 or more kinds can be obtained. Although what kind of isomers and mixtures are obtained varies depending on the reaction conditions, usually, a mixture of all these 10 isomers is obtained. In particular, when substantially no chiral component is contained in the reagents and solvents used in the production, and further other additives, all of the C ₆₀ derivatives having an enantiomeric relationship in each positional isomer are 1: It produces | generates by the ratio of 1, and what is called a racemate is obtained. In this case, in ¹ H-NMR analysis, the two hydrogen atoms directly bonded to the C ₆₀ skeleton are not equivalent in any positional isomer, and the single-line peak corresponding to these two types of hydrogen atoms. When two types of two pairs usually appear and peaks do not overlap each other, a total of 10 single lines are observed.

In addition, in the method for producing the 8-added C ₆₀ derivative of the present invention, the 10-added C ₆₀ derivative described below is by-produced together with the 8-added C ₆₀ derivative of the present invention.
The 10-addition C ₆₀ derivative is a compound having 10 organic groups R on the C ₆₀ skeleton. Although the relative position of each organic group R is not particularly limited, it is usually a 10-fold addition C ₆₀ dihydro derivative having two 5-fold addition partial structures (D) on the C ₆₀ skeleton.

Of the 10-added C ₆₀ derivatives, the 10-added C ₆₀ dihydro derivative described in Patent Document 3 as shown in the following structural diagram (2) is most preferable.

However, the relative positions of the two hydrogen atoms directly bonded to the C ₆₀ skeleton are not usually limited. In the figure, each hydrogen atom is bonded to any carbon atom of the cyclopentadienyl ring to which each hydrogen atom is bonded. May be. Therefore, the 10-fold addition C ₆₀ derivative produced as a by-product by the method for producing the 8-fold addition C ₆₀ derivative of the present invention has three types of stereoisomers based on the bonding position of the hydrogen atom even when the organic groups R are all the same. Is possible. Usually, a 10-fold addition C ₆₀ derivative produced as a by-product in the method for producing an 8-fold addition C ₆₀ derivative of the present invention is obtained as a mixture of these positional isomers. ^{In 1} H-NMR analysis, the hydrogen atom directly bonded to the C ₆₀ skeleton of the 10-addition C ₆₀ derivative is equivalent in any regioisomer, and if the peaks do not overlap with each other, the singlet based on this Three types of line peaks are observed.

The 10-added _C60 derivative produced as a by-product here is described in Patent Document 3 and Non-Patent Document 7, but the conventional production method reported therein _firstly synthesizes 5-added C60, This is a multi-step process in which a hydrogen atom directly bonded to the C ₆₀ skeleton is converted into a cyano group, a pentaaddition reaction of an organic group is further performed, and finally the cyano group is removed.

On the other hand, according to the production method of the 8-addition C ₆₀ derivative of the present invention, the organocopper reagent RCu is merely reacted with fullerene C ₆₀ under specific conditions, compared with the conventional production method. A 10-fold addition C ₆₀ derivative can be produced very easily in one step. Therefore, the method for producing an 8-fold addition C ₆₀ derivative of the present invention is also useful as a method for producing a 10-fold addition C ₆₀ derivative.

The 8 polyaddition C ₆₀ derivative production method of the present invention, the reaction conditions, varying the production ratio of 8 polyaddition C ₆₀ derivative (8 polyaddition C ₆₀ derivatives of the present invention) and 10 polyaddition C ₆₀ derivatives Can do. Therefore, an appropriate reaction condition may be set according to the type or ratio of the target C ₆₀ derivative. The total yield of the 8-added C ₆₀ derivative and the 10-added C ₆₀ derivative is usually 8 mol% or more and usually 80 mol% or less.

Further, when the production method of the 8-addition C ₆₀ derivative of the present invention is applied to the 5-addition C ₆₀ derivative described in Patent Documents 1 and 2 and Non-Patent Document 4, that is, the organic copper is added to the 5-addition C ₆₀ derivative. Even when the reagent RCu is reacted, an 8-fold addition C ₆₀ derivative and a 10-fold addition C ₆₀ derivative are obtained in the same manner. In this case, the organic group in the raw material (organic group possessed by the 5-addition C ₆₀ derivative) and the newly introduced organic group (organic group introduced by the organic copper reagent RCu) can be different. Therefore, it is also possible to produce a 10-fold addition C ₆₀ derivative selectively having a 5-fold addition partial structure (5-fold addition site) of two different organic groups.

In the method for producing an octaaddition C ₆₀ derivative of the present invention, the target octaaddition C ₆₀ derivative or 10 polyaddition C ₆₀ derivative can be obtained as a mixture of a plurality of isomers. The target derivative or its isomer can also be separated by a method such as silica gel column chromatography or HPLC.

8 polyaddition C ₆₀ derivatives or 10 polyaddition C ₆₀ derivative obtained by the production method of 8 polyaddition C ₆₀ derivatives of the present invention is a fullerene derivative having a specific structure having an organic group in a particular position, electronic materials It is useful as a physiologically active substance, a structural unit for forming a nanostructure, and a raw material thereof. Furthermore 10 polyaddition C ₆₀ derivatives, as described in Patent Document 3 and Non-Patent Document 7, are also useful as a raw material of 10 polyaddition C ₆₀ derivative of the metal complex, 8 polyaddition C ₆₀ derivatives likewise It is useful as a raw material for the corresponding metal complex.

<6: Method for producing fullerene metal complex>
As a method for producing a fullerene metal complexes of the present invention (6 polyaddition C ₇₀ metal complex and 8 polyaddition C ₆₀ metal complex) is not particularly limited, for example, 6 polyaddition C ₇₀ derivatives described above and A method of treating the 8-addition C ₆₀ derivative with a base and further treating with a metal salt as necessary is mentioned. That is, after the fullerene C ₇₀ or C ₆₀ and organocopper reagents and 6 polyaddition C ₇₀ derivatives by reacting mono- and / or 8 polyaddition C ₆₀ step of producing a derivative, C ₇₀ obtained in the process A 6-addition _C70 metal complex and / or an 8-addition _C60 metal complex can be produced by treating the derivative and / or the 8-addition _C60 derivative with a base and further treating with a metal salt as necessary. it can. In the following description, in particular, as an example the case of producing a 6 polyaddition C ₇₀ metal complex 6 polyaddition C _70-dihydro derivative as a raw material will be described in detail.

Specific procedures, first, the processing by base 6 polyaddition C _70-dihydro derivative. As the base, a compound having an alkali metal belonging to Group 1 of the periodic table (alkali metal compound) is usually used. Examples of the alkali metal compound include alkali metal hydrides such as LiH, NaH, and KH, and alkali metal alkoxides such as KO ^t Bu, NaOMe, and LiOMe. Here, ^t Bu represents a tertiary butyl group, and Me represents a methyl group.

Reactions 6 polyaddition C _70-dihydro derivative is treated with a base is generally carried out in ethereal solvent such as THF. Base, to 6 polyaddition C ₇₀ derivatives of the raw materials, usually one equivalent or more in molar ratio, all of the triple additional partial structure (A), 2 eq when coupling the group ML _n in (B) In addition, usually 20 equivalents or less are used. Thus, hydrogen atoms directly bonded to C ₇₀ backbone of 6 polyaddition C _70-dihydro derivative is replaced by an alkali metal, 6 polyaddition C ₇₀ derivatives - alkali metal complex is formed.

Incidentally, triple additional partial structure base has six polyaddition C ₇₀ derivatives of the raw material (A), in the case where less than (B), i.e., the base is less than 2 equivalents relative to 6 polyaddition C ₇₀ derivatives of the raw material In some cases, one hydrogen atom of two triple addition partial structures of the hexaaddition _C70 derivative is substituted with an alkali metal, and the other hydrogen atom is not substituted. It is possible to control the structure.

Furthermore, when used as plural kinds as the base, two triple additional partial structure having six polyaddition C ₇₀ derivative (A), it is possible to couple different types of base ML _n in (B), which It is also possible to control the structure using.

If the product is a 6 polyaddition C ₇₀ metal complex of interest, by removing the excess base by filtration or decantation from the solution after the reaction, a solution of 6 polyaddition C ₇₀ metal complex of interest can get.

On the other hand, an alkali metal other than the metal elements, i.e. in the synthesis of 6 polyaddition C ₇₀ metal complex having a metal belonging to 2-10 of the periodic table is 6 polyaddition C ₇₀ obtained in the base treatment derivatives - with respect to the alkali metal complexes, further may be reacted with the group 2 to 10 metals salts corresponding to the structure 6 polyaddition C ₇₀ metal complex of interest. Examples of the Group 2 to 10 metal salt used here include a metal compound having a leaving group such as a metal halide, or a cationic metal complex.

The amount of Group 2 to 10 metals salts, the bases 6 polyaddition C ₇₀ derivative obtained by the process - if less than the base ML _n alkali metal complexes, resulting in the base treatment 6 polyaddition C ₇₀ derivative was - to become the only part of the group ML _n of alkali metal complexes not substituted in group 2 to 10 metals salts, it is also possible to structure controlled by utilizing this .

Further, when a plurality of kinds of metal salts are used, it is possible to bond different types of groups ML _n in the two triple addition partial structures (A) and (B) of the hexaaddition C ₇₀ derivative, Structural control using this is also possible.

In addition, when synthesizing a hexaaddition _C70 metal complex having a ligand L, the target ligand L or its precursor is allowed to coexist in the reaction system during the treatment with a base, or An alkali metal compound having the ligand L may be used. Further, in the case of synthesizing 6 polyaddition C ₇₀ metal complex having a metal element other than the alkali metal, 6 polyaddition C ₇₀ derivatives - in the step of reacting an alkali metal complex and the 2-10 metal compound, object The ligand L or its precursor may be coexisted in the reaction system.

As described above, isomers exist in the hexaaddition _C70 metal complex of the present invention. In the production method of the present invention, a simple substance or a mixture of these isomers is obtained. Although what kind of isomers and mixtures are obtained varies depending on the reaction conditions, usually a mixture of these isomers is obtained.

  When the obtained mixture has an optical isomer, only one enantiomer is resolved by a general optical resolution method such as high performance liquid chromatography using a chiral column (hereinafter abbreviated as “HPLC” where appropriate). And can be isolated.

Metal complexes of 6 polyaddition C ₇₀ derivative obtained by the process of the present invention is a six organic groups and 1-2 metal atoms are added derivatives to a specific relative position of the C ₇₀ skeleton, the catalyst, It is useful as an electronic material, a physiologically active substance, a structural unit for forming a nanostructure, or a raw material thereof.

Further, the octaaddition C ₆₀ metal complex can also be produced by treating the octaaddition C ₆₀ dihydro derivative with a base in the same manner as the above hexaaddition C ₇₀ metal complex. The operation, conditions, type of base and metal salt, structure control method, etc. for the treatment with the base and metal salt are the same as those for the hexaaddition _C70 metal complex.

The product identification and the optical resolution method when the obtained mixture is an optical isomer can also be carried out in the same manner as in the case of the hexaadded _C70 metal complex.

Furthermore, the metal complex of the 8-addition _C60 derivative obtained by the production method of the present invention is similar to the 6-addition _C70 metal complex as a catalyst, an electronic material, a physiologically active substance, a structural unit for forming a nanostructure, etc. Or it is useful as those raw materials.

<7: Alkyl group introduction reaction to fullerene metal complex>
A part of the fullerene metal complex described in the section <3: Fullerene metal complex> produced by the method described in the section <6: Production method of fullerene metal complex> described above is further added as a raw material. The reaction can be carried out, whereby a new fullerene metal complex having an increased number of additional groups can be obtained.
The raw material used here is a _C70 metal complex, and its skeleton is a fullerene metal complex having two of the following triple addition metal complex partial structures (C) on the _C70 skeleton.

As the metal atom of the fullerene metal complex, a conventionally known fullerene metal complex having low reactivity of a cyclopentadienyl moiety, that is, a stable fullerene metal complex is used. Therefore, a complex of group 1 metal is not preferable, and usually a metal atom is a transition metal of group 2 to group 10, more preferably group 4 to group 10, more preferably a group 8 to group 10 late transition metal, Particularly preferred are group 8 transition metals. Specifically, Ru and Fe are most preferable. It is considered that the electronic state on the fullerene skeleton changes depending on the type of metal, and the reactivity is thereby determined. The preferred ligand L _{n in} the case of the most preferred Group 8 transition metal is a substituted and unsubstituted cyclopenta that forms a stable complex as described in the section <6: Production method of fullerene metal complex>. Dienyl ligand. In the case of other ligands, some are not preferred because they are eliminated under the reaction conditions.

  The reaction reagent is not particularly limited and may be any type as long as a new organic group can be introduced into the fullerene skeleton. Usually, an organometallic reagent such as an organolithium reagent, a Grignard reagent, an organocopper reagent, and an organozinc reagent. Is used. Among them, the organic copper reagent described in the section <5: Production method of fullerene derivative> described above is preferable, and the organic copper reagent is reacted with the fullerene metal complex in the presence of pyridine in the same manner as described therein. Is most preferred. In this case, the type of organic group, the preparation method of the organic copper reagent, the reaction method, the reaction termination method, and the post-treatment method are as described in the section of <5: Production method of fullerene derivative>.

The novel fullerene metal complex obtained by this method is a binuclear complex in the 7-addition _C70 metal complex described in the section of <4: 7-addition _C70 metal complex> described above. adding a metal complex moiety (C) 2 bract and an organic group R 'having 1 to 20 carbon atoms, a 7 polyaddition C ₇₀ metal complex having one hydrogen atom on the C ₇₀ skeleton.

More preferably, the following partial structure (F), a C ₇₀ metal complex having one or on C ₇₀ skeleton of (G). In the figure, R ′ is a newly introduced organic group.

  The new fullerene metal complex obtained by this production method is expected to exhibit an electronic behavior different from that of the raw material fullerene metal complex.

Since the 7-added C ₇₀ binuclear complex produced here has a C—H group on the fullerene skeleton, it is also useful as a raw material for synthesizing a further fullerene metal complex. For example, in some cases, a metal atom can be further introduced by carrying out a reaction similar to the method described in the section <5: Production method of fullerene derivative>. Specifically, the base described in the section <5: Production method of fullerene derivative> is allowed to act on the fullerene metal complex to generate a complex having a group 1 metal on the fullerene in the system. Thereafter, the target metal atom is allowed to act by acting the “metal compound having a leaving group such as a metal halide or a cationic metal complex” described in the section <5: Production method of fullerene derivative>. Can be introduced onto the fullerene skeleton.

At this time, the introduced metal atom is coordinated in a η ⁵ form on a 5-membered ring in which C—H is usually present as a raw material to form a stable complex. For example, in the 7-addition C ₇₀ binuclear complex obtained from the above-described 6-addition C ₇₀ metal complex which is a preferred form of the present invention, the position is specifically shown in the following partial structures (H) and (I). New metals are introduced.

There has been no report on a fullerene metal complex in which three metal atoms are coordinated in a η ⁵ type coordination on one fullerene skeleton like the metal complex obtained by the production method of the present invention described above. Since it is a unique compound with metal atoms coordinated to the density, a unique electronic behavior is expected. In addition, since bonds can be extended in three directions from one fullerene center via a metal atom, it is also useful as an element for the construction of a molecular-sized nanostructure.

The identification of each product in the present specification is, for example, ¹ H-nuclear magnetic resonance method (hereinafter abbreviated as “ ¹ H-NMR” as appropriate), ¹³ C-nuclear magnetic resonance method (hereinafter, appropriately referred to as “ ¹³ C— NMR ”) and, in some cases, mass spectrometry (hereinafter abbreviated as“ MS ”where appropriate) analysis or X-ray crystal diffraction.

EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not restrict | limited to a following example, In the range which does not deviate from the summary of this invention, it can change arbitrarily and can implement. In the present specification, “Ph” represents a phenyl group, “Me” represents a methyl group, “Et” represents an ethyl group, “Bu” represents a butyl group, and “ ^t Bu” represents a tertiary group. Represents a butyl group. Cp represents a cyclopentadienyl group.

Example 1: Synthesis of C ₇₀ Ph ₆ H ₂
To a solution of copper reagent CuBr · Me ₂ S (368 mg, 1.78 mmol) in pyridine (25.0 mL) was added Grignard reagent PhMgBr in THF (1.35 M, 1.32 mL, 1.78 mmol) at 26 ° C. The mixture was stirred at temperature for 10 minutes to synthesize a yellow suspension (organo copper reagent PhCu).

To the resulting yellow suspension, a solution of C ₇₀ (50.2 mg, 59.4 μmol) in degassed 1,2-Cl ₂ C ₆ H ₄ (25.0 mL) was added and stirred at 26 ° C. for 20 hours. . Thereafter, a 5% aqueous HCl solution was added to stop the reaction.

The product solution was dried over anhydrous MgSO ₄ , filtered through a SiO ₂ pad, concentrated to about 10 mL, and methanol (300 mL) was added thereto to obtain a dark red precipitate. This was thoroughly washed with methanol, ether and water, and dried under reduced pressure to give a crude product of C ₇₀ Ph ₆ H ₂ which is a hexaadded C ₇₀ derivative (65 mg, yield 85%, purity 70%). Got.

The obtained crude product of C ₇₀ Ph ₆ H ₂ was purified by HPLC separation (Buckyprep, 250 mm, toluene: isopropanol = 7: 3) to obtain a pure sample for analysis (31 mg, yield). 40%). A single crystal for X-ray crystal diffraction was obtained from the CS ₂ / ethanol solution.

A pure sample obtained by HPLC separation was subjected to ¹ H-NMR and MS analysis. The single crystal obtained from the CS ₂ / ethanol solution was analyzed by X-ray crystal diffraction. The results are shown below.

[Analytical result of C ₇₀ Ph ₆ H ₂ ]
¹ H-NMR (400 MHz, CDCl ₃ ) δ 4.747, 4.773, 4.850, 4.925 (Ratios of intensities = 1: 2: 2: 6, s, 2H), 7.10-7.45 (12H), 7.55-7.75 (6H) , 7.85-7.89 (4H), 7.93-8.05 (8H)
APCI-TOF MS calcd for C ₁₀₆ H ₃₂ [(M + H) ⁺ ]; 1306.2616, found m / z = 1306.2532

As a result of the analysis, the obtained substance by the present embodiment, it was confirmed that the sixfold additional C ₇₀ derivative C ₇₀ Ph ₆ H ₂ having the above structure.

<Example 2: Synthesis of _{C 70 (4-n-Bu} -C 6 H 4) 6 H 2>
367 mg of copper reagent CuBr · Me ₂ S was used, and Ar ¹ MgBr in THF as a Grignard reagent (Ar ¹ = 4-n-C ₄ H ₉ -C ₆ H ₄ , 0.71 M, 2.51 mL, 1. synthesizing an organic copper reagent Ar ¹ Cu with 78 mmol), except that was carried over the reaction of the organic copper reagent Ar ¹ Cu and C ₇₀ 24 hours in the same manner as in example 1, 6 polyaddition C ₇₀ derivatives _{C 70 (4-n-C} 4 H 9 -C 6 H 4) of the ₆ H ₂ crude product is (89 mg, 92% yield, purity 83%) was prepared.

The obtained crude product of C ₇₀ (4-n-C ₄ H ₉ —C ₆ H ₄ ) ₆ H ₂ was separated by HPLC separation (Buckyprep, 250 mm, toluene: isopropanol = 7: 3) in the same manner as in Example 1. To give a pure sample for analysis (58 mg, 60% yield).

A pure sample obtained by HPLC separation was subjected to ¹ H-NMR and MS analysis. The results are shown below. As a result of analysis, it was confirmed that the obtained sample was C ₇₀ (4-n-C ₄ H ₉ -C ₆ H ₄ ) ₆ H ₂ which is a 6-addition C ₇₀ derivative.

_{[C 70 (4-n-} C 4 H 9 -C 6 H 4) of the ₆ H ₂ Analysis Results
¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.83-1.05 (18H), 1.22-1.41 (12H), 1.43-1.69 (12H), 2.10-2.73 (12H), 4.711, 4.737, 4.816, 4.890 (Ratios of intensities = 1: 2: 2: 6, s, 2H), 7.00-7.12 (4H), 7.16-7.25 (8H), 7.43-7.49 (2H), 7.54-7.58 (2H), 7.72-7.77 (2H), 7.80-7.90 (6H)
APCI-MS m / z = 1636 (M ⁺ ); Anal.calcd for C ₁₂₀ H ₈₀ : C 94.70; H 5.30. Found: C 94.57; H 5.10

<Example 3: Synthesis of _{C 70 (4-Me-C} 6 H 4) 6 H 2>
367 mg of copper reagent CuBr · Me ₂ S was used, and Ar ² MgBr in THF (Ar ² = 4-CH ₃ —C ₆ H ₄ , 1.04 M, 1.71 mL, 1.78 mmol) was used as the Grignard reagent. The organic copper reagent Ar ² Cu was synthesized and the reaction between the organic copper reagent Ar ² Cu and C ₇₀ was carried out over 24 hours in the same manner as in Example 1 except that C ₇₀ was a hexaaddition C ₇₀ derivative. A crude product of (4-CH ₃ —C ₆ H ₄ ) ₆ H ₂ was prepared.

The obtained crude product of C ₇₀ (4-CH ₃ -C ₆ H ₄ ) ₆ H ₂ is subjected to HPLC separation (Buckyprep, 250 mm, toluene: isopropanol = 7: 3) in the same manner as in Example 1. To give a pure sample for analysis (32.6 mg, 40% yield).

A pure sample obtained by HPLC separation was subjected to ¹ H-NMR and MS analysis. The results are shown below. As a result of analysis, it was confirmed that the obtained sample was C ₇₀ (4-CH ₃ -C ₆ H ₄ ) ₆ H ₂ which is a hexaaddition C ₇₀ derivative.

_{[C 70 (4-CH 3} -C 6 H 4) of the ₆ H ₂ Analysis Results
¹ H-NMR (400 MHz, CDCl ₃ ) δ 2.27-2.43 (18H), 4.710, 4.738, 4.802, 4.882 (Ratios of intensities = 1: 2: 2: 6, s, 2H), 7.00-7.30 (6H) , 7.40-7.55 (m, 6H), 7.75-7.89 (m, 12H)
APCI-MS m / z = 1389 (M ⁺ )

<Example 4: Synthesis of K ₂ {C ₇₀ [4-CH ₃ C ₆ H ₄ ] ₆ }>
C ₇₀ (4-CH ₃ C ₆ H ₄ ) ₆ H ₂ (6.1 mg, 0.044 mmol) which is a 6-addition C ₇₀ derivative and KH (21 mg, 0.53 mmol) which is an alkali hydride under argon In a Schlenk tube and freshly distilled THF (6.0 mL) was added. Hydrogen gas evolved immediately and the color of the solution changed from red to black. After stirring for 15 minutes, insoluble matters were removed by centrifugation, and K ₂ {C ₇₀ [4-CH ₃ C ₆ H ₄ ] ₆ }, which is a metal complex, was obtained.

THF was distilled off, and freshly distilled DMF (N, N-dimethylformamide) -d ₇ (0.5 mL) was added to prepare a sample for NMR measurement. The measurement results of ¹ H-NMR and ¹³ C-NMR are shown below. As a result of analysis, it was confirmed that the obtained product was K ₂ {C ₇₀ [4-CH ₃ C ₆ H ₄ ] ₆ }, which is a fullerene metal complex.

[Analytical result of K ₂ {C ₇₀ [4-CH ₃ C ₆ H ₄ ] ₆ }]
¹ H-NMR (400 MHz DMF-d ₇ ): δ 2.20 (s, 3H, CH ₃ ), 2.28 (s 3H, CH ₃ ), 2.29 (s, 3H, CH ₃ ), 6.94 (d, J _HH = 8.0 Hz, 2H, C ₆ H ₅ ), 7.04 (d, J _HH = 8.0 Hz, 2H, C ₆ H ₅ ), 7.10 (d, J _HH = 7.6 Hz, 2H, C ₆ H ₅ ), 7.76 (d , J _HH = 8.0 Hz, 2H, C ₆ H ₅ ), 7.95 (d, J _HH = 7.6 Hz, 2H, C ₆ H ₅ ), 8.00 (d, J _HH = 8.0 Hz, 2H, C ₆ H ₅ )
¹³ C-NMR (100 MHz DMF-d ₇ ): δ 21.18 (2C, CH ₃ ), 21.22 (2C, CH ₃ ), 21.23 (2C, CH ₃ ), 56.63 (2C, C ₇₀ ), 58.76 (2C, C ₇₀ ), 61.20 (2C, C ₇₀ ), 118.18 (2C), 120.30 (2C), 128.06 (2C), 128.40 (4C, C ₆ H ₄ ), 128.52 (4C, C ₆ H ₄ ), 128.60 (4C , C ₆ H ₄ ), 128.99 (4C, C ₆ H ₄ ) 129.07 (4C C ₆ H ₄ ), 129.19 (4C, C ₆ H ₄ ) 129.22 (4C, C ₆ H ₄ ), 129.37 (4C, C ₆ H ₄ ), 130.75 (2C) 132.10 (2C), 133.04 (2C), 133.18 (2C), 133.77 (2C) 134.08 (2C), 134.49 (2C), 135.20 (2C), 135.35 (2C), 138.68 (2C) ), 139.03 (2C), 142.11 (2C), 142.34 (2C), 143.12 (2C), 143.37 (2C), 143.51 (2C), 143.91 (2C), 145.46 (2C), 146.02 (2C), 146.88 (2C) ), 147.46 (2C), 147.58 (2C), 147.75 (2C), 148,32 (2C), 148.63 (2C), 149.33 (2C), 149.38 (2C), 150.00 (2C), 152.35 (2C), 154.32 (2C), 158.57 (2C), 166.68 (2C), 170.78 (2C)
In the ¹³ C-NMR, two peaks of the C ₇₀ skeleton were detected in a state where they overlapped with other peaks.

Example 5 Synthesis of C ₆₀ Ph ₈ H ₂
To a black suspension obtained by mixing a copper reagent CuBr · Me ₂ S (1.16 g, 5.67 mmol), C ₆₀ (100 mg, 0.139 mmol) and pyridine (20 mL), a Grignard reagent PhMgBr in THF ( 0.97M, 5.70 mL, 5.67 mmol) was added at 0 ° C. The mixture was heated to 23 ° C. and stirred at 23 ° C. for 24 hours, a saturated NH ₄ Cl aqueous solution (0.10 mL) was added to stop the reaction, and the solvent was distilled off under reduced pressure.

The resulting mixture was diluted with chlorobenzene (50 mL) and filtered through a silica gel pad. The resulting orange solution was concentrated and separated by HPLC (Develosil, RPFullerene, 250 mm, toluene: acetonitrile = 2: 3). The yellow fraction of C ₆₀ Ph ₁₀ H ₂ and the red fraction of C ₆₀ Ph ₈ H ₂ were collected and concentrated. Each was precipitated by adding methanol, and C ₆₀ Ph ₁₀ H ₂ (35.3 mg, 17% yield) was used as a mixture of three regioisomers to give C ₆₀ Ph ₈ H ₂ (77.1 mg, 36% yield). ) As a mixture of five regioisomers.
The obtained mixture was subjected to ¹ H-NMR and MS analysis, respectively. The results are shown below. As a result of the analysis, it is C ₆₀ Ph ₁₀ H ₂ is a C ₆₀ Ph ₈ H ₂ and 10 polyaddition C ₆₀ derivatives are those obtained eight polyaddition C ₆₀ derivative was confirmed.

[Analysis result of C ₆₀ Ph ₁₀ H ₂ ]
¹ H-NMR (400 MHz CDCl ₃ ): δ 5.506, 5.510, and 5.528 (s, 2H, C ₆₀ -H), 7.10-7.25, 7.30-7.37, 7.42-7.47, 7.62-7.68 and 7.80-7.87 (m , 50H, C ₆ H ₅ ,)
APCI-TOF MS calcd for C ₁₂₀ H ₅₂ [(M + H) ⁺ ]; 1494.4231, found m / z = 1494.4181

[Analytical result of C ₆₀ Ph ₈ H ₂ ]
¹ H-NMR (400 MHz CDCl ₃ ): δ 5.084, 5.157, 5.193, 5.263, 5.275, 5.399, 5.439, 5.513, and 5.513 (s, 2H, five signals of C ₆₀ -H), 7.00-7.36, 7.40- 7.50, 7.55-7.71, 7.80-7.82, 7.86-7.87, 8.09-8.11, and 8.17-8.20 (m, 40H, C ₆ H ₅ )
APCI-MS (-) m / z = 1338 (M -)

Example 6 Synthesis of C ₆₀ (2-naphthyl) ₈ H ₂
The amount of copper reagent CuBr · Me ₂ S used was 216 mg (1.05 mmol), the amount of C ₆₀ used was 25.0 mg (0.035 mmol), the amount of pyridine used was 5 mL, and Grignard reagent (2-naphthyl) ) A solution of MgBr in THF (0.80 M, 1.3 mL, 1.05 mmol) was added at −40 ° C., stirring was carried out at 27 ° C. for 18 hours, and the amount of saturated aqueous NH ₄ Cl solution added to stop the reaction was reduced to 0.00. A red fraction and a yellow fraction were obtained in the same manner as in Example 5 except that 15 mL of toluene was used to dilute the resulting mixture.

The obtained red and yellow fractions were concentrated, and C ₆₀ (2-naphthyl) ₈ H ₂ (24 mg, 35% yield) was obtained from the red fraction as a mixture of three regioisomers. From the yellow fraction, C ₆₀ (2-naphthyl) ₁₀ H ₂ (4.0 mg, 5.1% yield) was obtained as a mixture of five regioisomers.

The obtained mixture was subjected to ¹ H-NMR and MS analysis, respectively. The results are shown below. Analysis revealed that those obtained is _{C 60 (2-naphthyl) 10} H 2 is a _{C 60 (2-naphthyl) 8} H 2 and 10 polyaddition C ₆₀ derivative is 8 polyaddition C ₆₀ derivatives confirmed.

[Analytical result of C ₆₀ (2-naphthyl) ₁₀ H ₂ ]
¹ H-NMR (400 MHz CDCl ₃ ): δ 5.866, 5.872, 5.896 (s, 2H, C ₆₀ -H of three isomers), 7.13-7.27, 7.35-7.43, 7.46-7.51, 7.65-7.68, 7.75-7.80 , 7.83-7.86, 7.99-8.08, 8.13-8.17, 8.25-8.27, 8.47-8.50 (m, 70H, C ₆ H ₅ )
APCI-TOF MS calcd for C ₁₃₀ H ₇₁ O ₁₀ [(MH) ^- ]; 1991.5574, found m / z = 1991.5556

[Analytical result of C ₆₀ (2-naphthyl) ₈ H ₂ ]
¹ H-NMR (400 MHz CDCl ₃ ): δ 5.265, 5.332, 5.340, 5.378, 5.523, 5.534, 5.655, 5.704, 5.768 (s, 2H, C ₆₀ -H of five isomers), 6.93-7.43, 7.50-7.87 , 7.98-8.16, 8.23-8.40, 8.50-8.57 (m, 56H, C ₆ H ₅ )
APCI MS [(MH) ^- ]; m / z = 1737

<Example 7: Synthesis of _{C 60 (4-OMe-C} 6 H 4) 8 H 2>
The amount of copper reagent CuBr · Me ₂ S used was 216 mg (1.05 mmol), the amount of C ₆₀ used was 25.0 mg (0.035 mmol), the amount of pyridine used was 5 mL, and the Grignard reagent was (4-MeOC). ₆ H ₄ ) MgBr in THF (0.81 M, 1.2 mL, 1.05 mmol) is added at −38 ° C., stirring is carried out at 28 ° C. for 20 hours, and the amount of saturated aqueous NH ₄ Cl solution added to stop the reaction. In the same manner as in Example 5 except that 15 mL of toluene was used to dilute the resulting mixture and the ratio of toluene: acetonitrile in the separation by HPLC was 3: 7. And got a fraction.

The obtained red and yellow fractions were concentrated, and C ₆₀ (4-OMe-C ₆ H ₄ ) ₈ H ₂ (24 mg, 35%) was extracted from the three regioisomers from the red fraction. As a mixture, the yellow fraction was washed with methanol to obtain C ₆₀ (4-OMe-C ₆ H ₄ ) ₁₀ H ₂ (4.0 mg, 5.1%) as a mixture of five regioisomers. Got as.

The obtained mixture was subjected to ¹ H-NMR and MS analysis, respectively. The results are shown below. Analysis revealed that obtained is 8 polyaddition C ₆₀ derivative _{C 60 (4-OMe-C} 6 H 4) 8 H 2 , and C ₆₀ is a 10-fold additional C ₆₀ derivative (4-OMe-C ₆ H ₄ ) ₁₀ H ₂ was confirmed.

[Analytical result of C ₆₀ (4-OMe-C ₆ H ₄ ) ₁₀ H ₂ ]
¹ H-NMR (400 MHz CDCl ₃ ): δ 3.58-4.01 (m, 30H, CH ₃ ), 5.412, 5.415, 5.434 (s, 2H, C ₆₀ -H of three isomers), 6.69-6.79, 6.87-7.02 , 7.13-7.17, 7.23-7.32, 7.41-7.57, 7.59-7.65 7.67-7.83 (m, 40H, C ₆ H ₄ OMe)
APCI-TOF MS calcd for C ₁₃₀ H ₇₁ O ₁₀ [(MH) ^- ]; 1791.5055, found m / z = 1791.5047

[Analysis result of C ₆₀ (4-OMe-C ₆ H ₄ ) ₈ H ₂ ]
¹ H-NMR (400 MHz CDCl ₃ ): δ 3.69-3.96 (m, 24H, CH ₃ ), 5.026, 5.096, 5.102, 5.133, 5.178, 5.188, 5.314, 5.354, 5.428 (s, 2H, C ₆₀ -H of five isomers), 6.55-6.65, 6.67-6.80, 6.86-6.85, 6.89-7.00, 7.06-7.08, 7.18-7.30, 7.36-7.41, 7.43-7.53, 7.54-7.56, 7.59-7.67, 7.70-7.82, 7.99 -8.02, 8.08-8.11 (m, 40H, C ₆ H ₄ OMe)
APCI-MS [(MH) ^- ]; m / z = 1577

<Example 8: Synthesis of _{C 60 (4-Cl-C} 6 H 4) 8 H 2>
The amount of copper reagent CuBr · Me ₂ S used was 432 mg (2.1 mmol), the amount of C ₆₀ used was 50.0 mg (0.070 mmol), and Grignard reagent (4-ClC ₆ H ₄ ) MgBr in THF was used. (0.95M, 2.2 mL, 2.1 mmol) was added at −40 ° C., stirring was performed at 28 ° C. for 90 hours, and 40 mL of toluene was used to dilute the resulting mixture. A red fraction and a yellow fraction were obtained.

The obtained red fraction and yellow fraction were each concentrated, and C ₆₀ (4-Cl—C ₆ H ₄ ) ₈ H ₂ (8.0 mg, 7.0%) was extracted from the red fraction. Obtained as a solid which is a mixture of regioisomers, and from the yellow fraction C ₆₀ (4-Cl—C ₆ H ₄ ) ₁₀ H ₂ (2.5 mg, 2.0%) was obtained as a mixture of 5 regioisomers. Obtained as a solid.

The obtained mixture was subjected to ¹ H-NMR and MS analysis, respectively. The results are shown below. As a result of analysis, the resulting products were octaaddition C ₆₀ derivative C ₆₀ (4-Cl—C ₆ H ₄ ) ₈ H ₂ and 10 polyaddition C ₆₀ derivative C ₆₀ (4-Cl—C ₆ H ₄ ) _10. It was confirmed to be H ₂ .

[Analysis result of C ₆₀ (4-Cl—C ₆ H ₄ ) ₁₀ H ₂ ]
¹ H-NMR (400 MHz, CDCl ₃ ): δ 5,430, 5.450 (s, 2H, C ₆₀ -H of three isomers), 6.99-7.03, 7.09-7.13, 7.16-7.30, 7.35-7.41, 7.42-7.46, 7.51-7.63, 7.75-7.82, 7.99-8.01, 8.07-8.09 (m, 40H, C ₆ H ₄ Cl)
APCI-TOF MS calcd for C ₁₂₀ H ₄₁ ³⁵ Cl ₉ ³⁷ Cl [(MH) ^- ]; 1833.0068, found m / z = 1833.0064

[Analytical result of C ₆₀ (4-Cl—C ₆ H ₄ ) ₈ H ₂ ]
¹ H-NMR (400 MHz, CDCl ₃ ): δ 5.011, 5.083, 5.120, 5.142, 5.187, 5.193, 5.315, 5.356, 5.421, 5.445 (s, 2H, C ₆₀ -H of five isomers), 6.99-7.12, 7.15-7.30, 7.31-7.44, 7.51-7.56, 7.58-7.65, 7.69-7.71, 7.72-7.80, 7.99-8.01, 8.07-8.09 (m, 40H, C ₆ H ₄ Cl)
APCI-MS [(MH) ^- ]; m / z = 1609

<Example _{9: (4-CH 3 C} 6 H 4) 6 C 70 (RuCp) 2 manufacturing>
_{C 70 [4- (CH 3)} C 6 H 4] 6 H 2 (5.0mg, 3.6μmol) to THF solution (1.0 mL) of the base ^t BuOK in THF (4.0μL, 1. 0M, 4.0 μmol) was added. After 10 minutes, [CpRu (CH ₃ CN) ₃ ] PF ₆ (2.3 mg, 5.4 μmol) was added. After stirring for 5 minutes, the above operation was repeated.

Toluene (10 mL) was added to the reaction mixture, filtered directly through a SiO ₂ pad and concentrated. The resulting crude product was purified by HPLC separation (Buckyprep, 250 mm, toluene: hexane = 3: 7), and Ru ₂ C ₇₀ [4- (CH ₃ ) C ₆ H ₄ ] ₆ (C ₅ H ₅₎ was obtained ₂ (5.9mg, 95% yield). A single crystal for X-ray crystal structure analysis was obtained from the PhCl / methanol solution.

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR, and MS analysis. A single crystal obtained from the PhCl / methanol solution was analyzed by X-ray crystal diffraction. The results are shown below.

[result of analysis]
¹ H-NMR (500 MHz, CDCl ₃ ) δ 2.36 (s, 6H, CH ₃ ), 2.42 (s 6H, CH ₃ ), 2.46 (s, 6H, CH ₃ ), 3.83 (s, 10H, Cp), 7.14 (d, J _HH = 8.5 Hz, 4H, C ₆ H ₅ ), 7.20-7.27 (m, 8H, C ₆ H ₅ ), 7.66 (d, J _HH = 8.0 Hz, 4H, C ₆ H ₅ ), 7.95 (d, J _HH = 8.0 Hz, 4H, C ₆ H ₅ ), 8.05 (d, J _HH = 8.0 Hz, 2H, C ₆ H ₅ )
¹³ C-NMR (125 MHz, CDCl ₃ ) δ 21.17 (2C, CH ₃ ), 21.21 (2C, CH ₃ ), 21.23 (2C, CH ₃ ), 54.74 (2C, C ₇₀ ), 56.43 (2C, C ₇₀ ), 58.78 (2C, C ₇₀ ), 74.02 (10C, C ₅ H ₅ ), 92.97 (2C, FCp), 93.70 (2C, FCp), 96.01 (2C, FCp), 96.66 (2C, FCp), 105. 11 (2C, FCp), 126.95 (2C), 128.12 (4C, C ₆ H ₄ ), 128.15 (4C, C ₆ H ₄ ), 128.25 (4C, C ₆ H ₄ ), 128.51 (4C, C ₆ H ₄ ) 128.68 (4C C ₆ H ₄ ), 128.72 (4C, C ₆ H ₄ ), 131.67 (2C) 133.55 (2C), 134.17 (2C), 136.20 (2C), 136.62 (2C) 136.85 (2C), 136.99 ( 2C), 138.00 (2C), 141.66 (2C), 142.51 (2C), 142.56 (2C), 142.85 (2C), 142.98 (2C), 143.87 (2C), 145.00 (2C), 145.44 (2C), 145.93 ( 2C), 146.17 (2C), 146.74 (2C), 147.17 (2C), 147.30 (2C), 147.70 (2C), 148.70 (2C), 148.74 (2C), 148.77 (2C), 149.53 (2C), 149.64 ( 2C), 150.97 (2C), 151.57 (2C), 151.61 (2C), 158.87 (2C), 163.14 (2C)
APCI-TOF MS calcd for C ₁₂₂ H ₅₃ ¹⁰² Ru ₂ [(M + H) ⁺ ]; 1721.2234, found m / z = 1721.2249

The structure of the synthesized title compound was clarified by ¹ H-NMR, ¹³ C-NMR, MS, and X-ray crystal structure analysis of a single crystal obtained from the PhCl / methanol system. The title compound was found to be a mixture of enantiomers.

<Example _{10: (4-MeC 6 H} 4) 7 C 70 H (RuCp) 2 manufacturing>

Copper reagent CuBr · SMe ₂ (78 mg, 0.35 μmol) and Ru ₂ C ₇₀ [4- (CH ₃ ) C ₆ H ₄ ] ₆ (C ₅ H ₅ ) ₂ (20 mg, 12 μmol) in pyridine (4.0 mL) ) A solution of Grignard reagent ArMgBr (Ar = (4-CH ₃ ) C ₆ H ₄ , 0.82M, 0.43 μL, 0.35 μmol) in THF was added to the solution at 0 ° C., and the mixture was stirred at this temperature for 5 minutes. Thereafter, the mixture was stirred at 50 ° C. for 12 hours, and 5% HCl aqueous solution was added to stop the reaction. The product was dried over anhydrous MgSO ₄ , filtered through a SiO ₂ pad and concentrated. The resulting crude product was purified by HPLC separation (Buckyprep, 250 mm, toluene: hexane = 3: 7), and Ru ₂ {C ₇₀ [4- (CH ₃ ) C ₆ H ₄ ] ₇ H}. (C ₅ H ₅ ) ₂ (18 mg, 86% yield) was obtained. A single crystal for X-ray crystal structure analysis was obtained from a PhCl / methanol solution.

The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR, and MS analysis. A single crystal obtained from the PhCl / methanol solution was analyzed by X-ray crystal diffraction. The results are shown below.

[result of analysis]
¹ H-NMR (500 MHz, CDCl ₃ ) δ 2.36 (s, 3H, CH ₃ ), 2.37 (s, 3H, CH ₃ ), 2.38 (s, 3H, CH ₃ ), 2.41 (s, 3H, CH ₃ ), 2.43 (s, 3H, CH ₃ ), 2.44 (s, 3H, CH ₃ ), 2.50 (s, 3H, CH ₃ ), 3.84 (s, 5H, Cp), 3.91 (s, 5H, Cp), 5.74 (s, 1H, C ₇₀ -H), 7.07-7.20 (m, 8H, C ₆ H ₄ ), 7.25-7.28 (m, 8H, C ₆ H ₄ ), 7.61 (d, J _HH = 8.0 Hz, 4H, C ₆ H ₄ ), 7.76-7.80 (m, 4H, C ₆ H ₄ ), 7.83-7.89 (m, 4H, C ₆ H ₄ ), 7.99 (d, J _HH = 7.5 Hz, 2H, C ₆ H ₄ ), 7.80 (d, J _HH = 8.0 Hz, 2H, C ₆ H ₄ ), 7.82-8.02 (m, 6H, C ₆ H ₄ ), 8.14 (d, J _HH = 7.5 Hz, 2H, C ₆ H ₄ )
¹³ C-NMR (125 MHz, CDCl ₃ ) δ 21.08 (1C, CH ₃ ), 21.14 (1C + 1C + 1C, CH ₃ ), 21.18 (1C, CH ₃ ), 21.23 (1C + 1C, CH ₃ ), 54.85 (1C, C ₇₀ ), 54.96 (1C, C ₇₀ ), 56.05 (1C, C ₇₀ ), 56.92 (1C, C ₇₀ ), 57.01 (1C, C ₇₀ ), 58.34 (1C, C ₇₀ ), 59.07 ( 1C, C ₇₀ ), 59.89 (1C, C ₇₀ ), 73.87 (5C, C ₅ H ₅ ), 73.95 (5C, C ₅ H ₅ ), 92.96 (1C, C ₇₀ ), 93.74 (1C, C ₇₀ ), 93.79 (1C, C ₇₀ ), 94.78 (1C, C ₇₀ ), 95.02 (1C, C ₇₀ ), 96.04 (1C + 1C, C ₇₀ ), 97.44 (1C, C ₇₀ ), 104.32 (1C, C ₇₀ ), 105.56 (1C, C ₇₀ ), 126.60, 127.08, 127.81, 127.90, 127.96, 128.06, 128.12, 128.26, 128.30, 128.37, 128.46, 128.49, 128.56, 128.80, 129.82, 130.10, 130.88, 133.20, 133.48, 133.94, 135.44, 136.45, 136.55, 136.62, 136.70, 136.72, 136.78, 136.90, 137.96, 138.56, 138.68, 140.27, 141.28, 141.51, 141.76, 142.12, 142.16, 142.39, 142.68, 142.85, 142.96, 143.20, 143.27, 143.31,18.63, 145.60, 145.69, 145.88, 146.37, 146.79, 146.99, 146.79, 146.99, 147.06, 147.32, 147.36, 147.57, 147.73, 148.16, 148.53, 148.56, 148.72, 149.42, 149.48, 150.08, 151.32, 152.73, 153.15, 153.27, 153.72, 153.80, 154.35, 154.79, 156.59, 158.15, 160.33, 160.97
APCI-TOF MS calcd for C ₁₂₉ H ₆₀ ¹⁰¹ Ru ¹⁰² Ru [(M) ⁺ ]; 1811.27943, found m / z = 1811.28280
In the ¹³ C-NMR, five signals at 120 to 161 ppm were detected in a state where they overlapped with other peaks.

The structure of the synthesized title compound was clarified by ¹ H-NMR, ¹³ C-NMR, MS, and X-ray crystal structure analysis of a single crystal obtained from the PhCl / methanol system. The title compound was found to be a mixture of enantiomers.

Example 11 Synthesis of Ru ₃ C ₇₀ [4- (CH ₃ ) C ₆ H ₄ ] ₇ (C ₅ H ₅ ) ₃ >
Ru ₂ {C ₇₀ [4- (CH ₃ ) C ₆ H ₄ ] ₇ H} (C ₅ H ₅ ) ₂ (70 mg, 39 μmol) in THF (7.0 mL) vs. ^t BuOK in THF (43 μL) , 43 μmol). After 10 minutes, [(C ₅ H ₅ ) Ru (CH ₃ CN) ₃ ] PF ₆ (19 mg, 43 μmol) was added. Toluene (10 mL) was added to the reaction mixture, filtered directly through a SiO ₂ pad and concentrated. Crystallization was carried out from a CH ₃ Cl / pentane solution to obtain Ru ₃ C ₇₀ [4- (CH ₃ ) C ₆ H ₄ ] ₇ (C ₅ H ₅ ) ₃ (41 mg, yield 54%). The synthesized compound was subjected to ¹ H-NMR, ¹³ C-NMR, and MS analysis. The results are shown below.

[result of analysis]
¹ H-NMR (500 MHz, CDCl ₃ ) δ 2.35 (s, 3H, CH ₃ ), 2.36 (s, 3H, CH ₃ ), 2.40 (s, 3H, CH ₃ ), 2.41 (s, 3H, CH ₃ ), 2.46 (s, 3H, CH ₃ ), 2.51 (s, 3H, CH ₃ ), 3.80 (s, 5H, Cp), 3.90 (s, 5H, Cp), 4.65 (s, 5H, Cp), 7.11 (d, J _HH = 8.0 Hz, 4H, C ₆ H ₄ ), 7.12-7.19 (m, 4H, C ₆ H ₄ ), 7.35 (d, J _HH = 8.0 Hz, 4H, C ₆ H ₄ ), 7.60 (d, J _HH = 7.5 Hz, 4H, C ₆ H ₄ ), 7.73 (d, J _HH = 7.5 Hz, 2H, C ₆ H ₄ ), 7.80 (d, J _HH = 8.0 Hz, 2H, C ₆ H ₄ ), 7.82-8.02 (m, 6H, C ₆ H ₄ ), 8.14 (d, J _HH = 7.5 Hz, 2H, C ₆ H ₄ )
¹³ C-NMR (125 MHz, CDCl ₃ ) δ 21.38 (1C + 1C + 1C, CH ₃ ), 21.43 (1C, CH ₃ ), 21.47 (1C, CH ₃ ), 21.50 (1C + 1C, CH ₃ ), 21.71 (1C, CH ₃ ), 55.03 (1C, C ₇₀ ), 55.38 (1C, C ₇₀ ), 56.48 (1C, C ₇₀ ), 56.87 (1C, C ₇₀ ), 58.22 (1C, C ₇₀ ), 59.54 ( 1C, C ₇₀ ), 59.99 (1C, C ₇₀ ), 72.22 (5C, C ₅ H ₅ ), 74.14 (5C, C ₅ H ₅ ), 74.17 (5C, C ₅ H ₅ ), 93.36 (1C, FCp) , 94.25 (1C, FCp), 94.42 (1C, FCp), 95.23 (1C, FCp), 95.82 (1C, FCp), 96.13 (1C, FCp), 96.45 (1C, FCp), 97.30 (1C, FCp), 97.40 (1C, FCp), 98.31 (1C, FCp), 104.23 (1C, FCp), 104.73 (1C, FCp), 104.82 (1C, FCp), 105.20 (1C, FCp), 110.93 (1C, FCp), 125.53 (1C), 126.63 (1C), 127.60 (1C), 128.13 (4C,), 128.32 (1C) 128.36 (1C), 128.46 (1C) 128.51 (1C), 128.57 (1C), 128.67 (1C), 128.72 ( 2C), 128.94 (1C) 129.15 (1C), 129.18 (1C), 129.27 (1C), 129.65 (1C), 130.57 (1C), 131.18 (1C), 133.53 (1C), 133.81 (1C), 136.06 (1C ), 136.53 (1C), 136.57 (1C), 136.62 (1C), 136.69 (1C), 136.76 (1C), 136.80 (1C), 136.87 (1C), 136.96 (1C), 137.47 (1C), 137.78 (1C) ), 138.12 (1C), 140.10 (1C), 140.14 (1C), 140.23 (1C), 141.61 (1C), 141.97 (1C), 142.23 (1C), 142.34 (1C), 142.75 (1C), 142.80 (1C), 142.96 (1C), 143.37 (1C), 143.47 (1C), 143.52 (1C), 143.52 (1C), 143.55 (1C), 145.23 (1C), 145.37 (1C), 146.38 (1C), 147.12 (1C), 147.19 (1C), 147.62 (1C), 147.65 (1C), 147.97 (1C), 148.24 (1C), 148.47 (1C), 149.14 (1C), 149.38 (1C), 149.64 (1C), 150.33 (1C), 151.24 (1C) 151.49 (1C), 151.84 (1C), 152.30 (1C), 152.60 (1C), 154.53 (1C), 155.52 (1C), 156.38 (1C), 156.77 (1C), 158.95 (1C), 165.35 (1C), 168.27 (1C)
APCI-TOF MS calcd for C ₁₃₄ H ₆₅ ¹⁰² Ru ₃ [(M + H) ⁺ ]; 1979.22167, found m / z = 1979.22819

The structure was confirmed by the above-mentioned ¹ H-NMR, ¹³ C-NMR, and mass spectrometry. That is, a signal of 7 methyl groups and a signal of 3 cyclopentadienyls were confirmed. From ¹³ C-NMR, 15 peaks corresponding to fullerene cyclopentadienyl were observed at 93.37 ppm to 110.93 ppm. This fact indicates that three rutheniums are coordinated to the fullerene skeleton in the η ⁵ type.

The fullerene derivatives of the present invention (C ₇₀ derivatives and C ₆₀ derivatives, and fullerene metal complexes) are useful in a wide range of industrial fields, such as catalysts, electronic materials, physiologically active substances, structural units for forming nanostructures, or It is suitably used as such raw materials.
In addition, the method for producing a fullerene derivative of the present invention is extremely industrially advantageous because the above-mentioned fullerene derivative can be efficiently produced with few steps.

Claims (8)

6 organic groups having 1 to 20 carbon atoms are bonded to the fullerene C ₇₀ skeleton ,
In the C ₇₀ on the backbone, the following partial structure (A), the partial structure (B), and, characterized by two have a partial structure selected from the group consisting of partial structure (C), fullerene derivatives.

{In said partial structure (A)-(C), R represents a C1-C20 organic group each independently. In the partial structure (C), M represents a metal atom, L represents a ligand of M, and n represents an integer of 0 or more. } The fullerene derivative according to claim 1, wherein the organic group is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent . The _C70 skeleton has a partial structure in which two partial structures selected from the group consisting of the partial structure (A), the partial structure (B), and the partial structure (C) are directly bonded. The fullerene derivative according to claim 1 or 2 . Seven organic groups having 1 to 20 carbon atoms are bonded to the fullerene C ₇₀ skeleton ,
On the fullerene C ₇₀ skeleton, and having two of the following partial structures (C), fullerene metal complexes.

{In the above partial structure (C), each R independently represents an organic group having 1 to 20 carbon atoms, M represents a metal atom, L represents a ligand of M, and n represents an integer of 0 or more. Represents. } Fullerene C ₇₀ 5. The skeleton has a partial structure selected from the group consisting of the following partial structure (F), partial structure (G), partial structure (H), and partial structure (I). The fullerene metal complex described in 1.

{In the above partial structures (F) to (I), R and R 'each independently represent an organic group having 1 to 20 carbon atoms, M and M' each independently represent a metal atom, and L and L ' 'Independently represents M or M', and n and n 'each independently represents an integer of 0 or more. } Fullerene C ₇₀ 1 piece skeleton respect, two or three metal atoms, characterized in that the coordinated claim 4 or 5 fullerene metal complex according. A method for producing a fullerene derivative according to any one of claims 1 to 3, further comprising a step of reacting fullerene with a monovalent organic copper reagent. The method for producing a fullerene derivative according to claim 7 , wherein the reaction is performed in the presence of pyridines .