Synthesis and metal complexation of a functional fullerene containing amine, phosphine, and pyridine coordinate groups

Accepted Manuscript Synthesis and metal complexation of a functional fullerene containing amine, phosphine, and pyridine coordinate groups Jang-Yun Yeh, Wen-Yann Yeh PII:

S0022-328X(16)30472-7

DOI:

10.1016/j.jorganchem.2016.10.025

Reference:

JOM 19669

To appear in:

Journal of Organometallic Chemistry

Received Date: 6 August 2016 Revised Date:

18 September 2016

Accepted Date: 15 October 2016

Please cite this article as: J.-Y. Yeh, W.-Y. Yeh, Synthesis and metal complexation of a functional fullerene containing amine, phosphine, and pyridine coordinate groups, Journal of Organometallic Chemistry (2016), doi: 10.1016/j.jorganchem.2016.10.025. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT H

N

N

H

H

Ph

Ph

Ph P Ph

N

Ru(CO)3 + Ru3(CO)12

C H Ru

N

+

C60

CH2

Ru (CO)3

Ru (CO)3

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(CO)3

P Ru (CO)2

PPh2(o-C6H4)(o-C5H4N)(C2H3NC60) has been prepared, which reveals versatile bonding manners upon

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coordination with ruthenium, tungsten, and osmium carbonyl complexes.

ACCEPTED MANUSCRIPT Synthesis and metal complexation of a functional fullerene containing amine, phosphine,

and pyridine coordinate groups☆

Jang-Yun Yeh, Wen-Yann Yeh*

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Department of Chemistry, National Sun Yat-Sen University, Kaohsiung 804, Taiwan

Abstract

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Treating C60 with o-(diphenylphosphino)benzaldehyde and o-aminomethylpyridine in refluxing

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o-dichlorobenzene affords a new fullerene derivative syn-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60) (1) in moderate yield. Compound 1 displays versatile coordination modes. Such that, reactions of 1 with Os3(CO)11(NCMe), W(CO)4(NCMe)2, and Ru3(CO)12 produce Os3(CO)11(η1-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (2), W(CO)4(η2-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (3), and Ru(CO)3(η3-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (4), respectively. Interestingly, heating 4 with Ru3(CO)12 leads to transfer of the fullerene addend to give C60

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and a tetraruthenium cluster complex (µ-H)Ru4(CO)11(µ4,η4-PPh2(o-C6H4)CH2NC(o-C5H4N)) (5). The

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structures of 1 and 5 have been determined by an X-ray diffraction study.

Keywords: Functional fullerene; Metal‒fullerene complex; C‒H activation; C‒C activation; Cluster complex. ___________________________ ☆

Dedicated to Professor Richard D. Adams for celebration of his 70th birthday.

*Corresponding author. E-mail address: [email protected] (W.-Y. Yeh)

ACCEPTED MANUSCRIPT

Introduction

Attachment of organometallic complexes to fullerenes is an important area within fullerene chemistry, due to its potential application in biological, magnetic, electronic, catalytic and optical devices [1–7]. With the development of an extensive organic chemistry of fullerenes, it is now possible to construct a variety of

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modified fullerenes that incorporate metal-binding groups into their structures [8–11]. The syntheses of such fullerene-containing ligands offer the potential to exploit the chemical reactivity, redox and electron-acceptor characteristics, photochemical behavior, electron-withdrawing properties, and novel structural features that a

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fullerene group provides [12–14]. Previously, the phosphinofullerenes C60H(PPh2) [15,16] and C60H2(PPh2)2 [17] were prepared through addition of phosphide nucleophiles to C60 and subsequent protonation of the

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resulting anion. We have recently reported the phosphine-functionalized fulleropyrrolidine molecule PPh2(o-C6H4)(C2H3NMe)C60 in according to the Prato’s method [18,19] and described it reactivity towards tungsten, ruthenium, osmium, and rhenium complexes [20,21]. In our continuing interest in the fullerene chemistry [22–25], herein we present the synthesis of a new polyfunctional fullerene molecule and report its

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Results and discussion

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complexation reactions with transition metal carbonyls to give products having different architectures.

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Preparation and characterization of 1

Treatment of C60 with o-(diphenylphosphino)benzaldehyde and o-aminomethylpyridine in refluxing o-dichlorobenzene affords a new fullerene derivative syn-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60) (1) in 46% yield after separation by TLC and crystallization from CS2/n-hexane. This reaction is highly stereospecific. Apparently, condensation reaction of the amine and aldehyde moieties forms an azomethine ylide intermediate by placing the two aromatic groups cis to the central H atom to reduce steric repulsions, which then undergoes [3+2] cycloaddition with one fullerene C＝C double bond to give 1 (Eq. (1)) [26]. The molecular structure of 1 is illustrated in Fig. 1. It appears that a pyrrolidine unit is fused with one 6:6-ring junction of C60 molecule. The distances C19–C27 1.573(7) Å, C20–C26 1.574(6) Å, and C26–C27 1.607(6) Å are typical C–C single

ACCEPTED bonds, while the remaining C–C lengths of C60 are av.MANUSCRIPT 1.38 Å (6:6-junctions) and 1.45 Å (6:5-junctions). The C26 and C27 atoms are sp3 hybridized and show a distorted tetrahedral bonding, where the C–C–C angles centered on the C26 atom are in the range 100.8(5)—114.4(4)º, and on the C27 atom are 101.3(4)—114.4(4)º. The pyrrolidine ring displays an envelope shape, of which the C19, C20, C26, and C27 atoms are coplanar

positions.

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[ Eq. (1) and Fig. 1 herein ]

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with the N1 atom 0.66 Å away from the plane, and the C18–C19 and C20–C21 bonds occupy the equatorial

Compound 1 forms a slightly air-sensitive, brown crystalline solid and should be stored under dinitrogen

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to avoid phosphine oxidation. The 1H NMR spectrum (Fig. 2) displays multiplets in 8.66—7.09 ppm for the aromatic protons, which can be assigned on the basis of an H,H-COSY experiment. The two methine C–H proton resonances appear as a singlet at 7.28 ppm (CHPy) and a doublet at 6.17 (4JP–H = 7 Hz) ppm, while the amine N–H proton gives a broad resonance at 4.16 ppm. The 31P resonance of 1 at –20.12 ppm is comparable

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to PPh2(o-C6H4)(C2H3NMe)C60 (–19.47 ppm) [20], but is ca. 30—50 ppm shielded relative to the fullerene-bound phosphine in (PPh2)C60H (30.1 ppm) and (PPh2)2C60H2 (27.62 and 15.29 ppm) [16,17].

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[Fig. 2 herein ]

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Complexation reactions of 1

Compound 1 is a multifunctional molecule to contain alkene, amine, phosphine, and pyridine binding groups. It is therefore of interest to investigate its coordination chemistry. Firstly, heating 1 with Os3(CO)11(NCMe) in toluene solution results in displacement of the labile acetonitrile ligand to afford Os3(CO)11(η1-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (2) in 39% yield after purification by TLC and crystallization from CS2/n-hexane (Eq.(2)). The IR spectrum of 2 in the carbonyl region displays an absorption pattern analogous to Os3(CO)11(η1-PPh2(o-C6H4)(C2H3NMe)C60) [20], of which the phosphine ligand is bonded to one equatorial site of a triosmium triangle. The 31P resonance of 2 at 0.02 ppm is 20.1 ppm

ACCEPTED MANUSCRIPT downfield of 1, consistent with decrease of electron density around phosphorus nucleus upon coordination with metal atom [27]. The 1H NMR spectrum of 2, shown in Fig. 3(a), displays the two methine proton resonances at 5.75 and 5.14 ppm and the amine proton resonance at 3.53 ppm, which are shielded by 1.53,

[ Eq. (2) and Fig. 3 herein ]

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1.03, and 0.63 ppm, respectively, compared to 1.

Reaction of 1 and W(CO)4(NCMe)2 took place in dichloromethane solution at ambient temperature. By

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replacing two labile acetonitrile ligands, W(CO)4(η2-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (3) was obtained in 67% yield after purification by TLC (Eq.(3)). The IR spectrum of 3 in the carbonyl region displays an

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absorption pattern similar to cis-W(CO)4(η2-PPh2(o-C6H4)CH＝NC2H4Py) [28], suggesting retention of the cis-W(CO)4LL´ configuration. The 31P resonance of 3 at 28.87 ppm shows 183W satellites with JW‒P = 225 Hz to indicate coordination of the phosphine group to the tungsten metal. The 1H NMR spectrum (Fig. 3(b)) shows isochronic of the two methine proton resonances to give a broad signal at 6.06 ppm, while the N–H

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resonance at 6.65 ppm is 2.5 ppm deshielded of 1. This large downfield shift for the amine proton strongly suggests coordination of the amine ligand to the tungsten atom. Thus, an energy-minimized configuration can be constructed for 3 (Fig. 4(a)), which contains a WPC3N metalla-heterocyclic ring. Attempts to

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coordinate the pyridine moiety to the tungsten atom by treating 3 with Me3NO or heating 3 in toluene were

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not successful, likely due to steric reasons that pyridine is far away from the tungsten center.

[ Eq. (3) and Fig. 4 herein ]

A dark green complex, characterized as Ru(CO)3(η3-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (4), was isolated in 44% yield from the reaction of 1 and Ru3(CO)12 in hot chlorobenzene (Eq. (4)). The molecular ion peak of 4 at m/z 1286 (102Ru) is the combination of 1 and one Ru(CO)3 moiety. The phosphine ligand is bonded to the ruthenium atom to give the 31P resonance at 17.43 ppm. The 1H NMR spectrum (Fig. 3(c)) displays the aromatic proton resonances in 8.53—7.09 ppm, the methine proton resonances at 6.72 (s) and

ACCEPTED MANUSCRIPT 5.73 (d, JP‒H = 7 Hz) ppm, and the amine proton resonance at 4.05 ppm, suggesting the amine and pyridine groups are not coordinate. We previously described that thermal reactions of PPh2(o-C6H4)(C2H3NMe)C60 and Ru3(CO)12 gave a green, monometallic complex Ru(CO)3(η3-PPh2(o-C6H4)(C2H3NMe)C60), of which the Ru(CO)3 group moiety is linked to the phosphorus atom and one C＝C double bond of the fullerene [20]. The IR spectrum of 4 in the carbonyl region (2078s, 2005vs, 1983s cm‒1) is basically identical to

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Ru(CO)3(η3-PPh2(o-C6H4)(C2H3NMe)C60) (2076s, 2004vs,1981s cm–1), and the 13C NMR spectrum of 4 presents two upfield signals at 75.6 and 71.8 ppm corresponding to M(η2-C60) carbon resonances [29‒32].

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Accordingly, a compatible structure can be drawn for 4, which is shown in Fig. 4(b).

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[ Eq. (4) herein ]

Reaction of 4 and Ru3(CO)12

Since compound 4 contains free amine and pyridine binding groups, we subsequently investigated its

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reactivity. Interestingly, further reaction of 4 and Ru3(CO)12 in chlorobenzene results in transfer of the fullerene addend to give C60 and a tetraruthenium cluster complex (µ-H)Ru4(CO)11(µ4,η4-PPh2(o-C6H4)CH2NC(o-C5H4N)) (5) in 17% yield (Eq. (5)). A single-crystal X-ray

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diffraction study was performed to reveal the structure of 5. There are two crystallographically independent molecules in the asymmetric unit, which are structurally equivalent and the molecular stereochemistry of one

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of these is illustrated in Fig. 5. The Ru2, Ru3, and Ru4 atoms form a triangle in which the Ru2–Ru4 bond length (2.9600(6) Å) is substantially longer than Ru2–Ru3 (2.7859(7) Å) and Ru3–Ru4 (2.7464(6) Å) lengths. The Ru1 atom is connected to Ru2 atom in the axial position, with Ru1–Ru2 2.8102(7) Å. The Ru2, Ru3, and Ru4 atoms are each bonded to three terminal carbonyl groups, while Ru1 atom has two, with Ru‒CO distances in the range 1.863(6)—1.945(6) Å, C‒O distances in the range 1.129(7)—1.158(7) Å, and Ru‒C‒O angles ranging from 163.9(6)º to 179.6(5)º. The four ruthenium atoms are associated with a PPh2(o-C6H4)CH2NC(o-C5H4N) link, of which the phosphine and pyridine groups are connected to the Ru1 atom with P1–Ru1 2.3518(15) Å and N2–Ru1 2.148(5) Å, the amide N1atom bridges the Ru1 and Ru4 atoms equally with N1–Ru1 2.156(4) Å and N1–Ru4 2.152(4) Å, and the alkylidene carbon C42 bridges the Ru2 and

ACCEPTED Ru3 atoms asymmetrically with C42–Ru2 2.197(6) ÅMANUSCRIPT and C42–Ru3 2.078(6) Å. The bridging hydride atom (detected by 1H NMR) is not located, but is likely spanning the Ru2–Ru3 edge on the basis of the 18-electron count for each metal center. It appears that this reaction carries out a methine (linked to Py) C–H bond activation on the metal cluster, and one hydrogen atom migrates from amine to the other methine center. However, it is not clear

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how the fullerene addend is transferred to the Ru4 cluster through C–C bond activation. The 1H NMR spectrum of 5 (Fig. 3(d)) displays the aromatic proton resonances in 7.92—6.31 ppm , the two diastereotopic methylene proton resonances at 4.03 and 3.71 ppm, and a sharp singlet at ‒17.48 ppm for the bridging hydride.

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The 31P resonance at 27.42 ppm is 10 ppm downfield of 4.

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[ Eq. (5) and Fig. 5 herein ]

Conclusion

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We have synthesized a new multifunctional fullerene derivative 1 from C60. Compound 1 can act as an η1-P ligand in 2, an η2-P,N chelating agent in 3, or as an η3-P,C2 ligand in 4, demonstrating a flexible binding capacity. Moreover, the fullerene addend of 1 can be transferred to a tetraruthenium cluster 5. The versatile

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bonding properties of 1 are applicable to split polynuclear complexes, or serve as a hemilabile chelating agent

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to alter the activity of the bound metal centers and may find an application in homogeneous catalytic systems.

Experimental

General methods

All manipulations were carried out under an atmosphere of purified dinitrogen with standard Schlenk techniques. Solvents were dried over appropriate reagents under dinitrogen and distilled immediately before use. W(CO)4(NCMe)2 [33] and Os3(CO)11(NCMe) [34] were prepared as described in the literature. C60 (99%; Bucky USA), o-(diphenylphosphino)benzaldehyde (Aldrich), o-aminomethylpyridine (Alfa Aesar), and

ACCEPTED Ru3(CO)12 (Strem) were used as received. PreparativeMANUSCRIPT thin-layer chromatographic (TLC) plates were prepared from silica gel (Merck). Infrared spectra were recorded on a Jasco FT/IR-4100 IR spectrometer. 1H and 31P NMR spectra were obtained on a Bruker Advance 300 spectrometer. Electrospray ionization (ESI) mass spectra were recorded on a Thermo Finnigan Triple Quadrupole mass spectrometer.

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Preparation of 1

C60 (2 g, 2.78 mmol), o-(diphenylphosphino)benzaldehyde (1.3 g, 4.48 mmol), o-aminomethylpyridine

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(600 mg, 5.55 mmol), and o-dichlorobenzene (150 ml) were placed in an oven-dried Schlenk flask equipped with a condenser. The solution was heated to reflux under a dinitrogen atmosphere for 10 min. The solvent was

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removed under vacuum, and the residue was subjected to TLC, with CS2/ethyl acetate (10:1, v/v) as eluent. The first purple band recovered C60 (160 mg) in 8%. Isolation of the material forming the major brown band afforded syn-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60) (1; 1.4 g, 1.27 mmol, 46%). 1H NMR (CD2Cl2, 25 ºC): 8.66 (d, 1H, JH‒H = 5 Hz, Py), 8.45 (m, 1H, C6H4), 8.08 (d, 1H, JH‒H = 8 Hz, Py), 7.82 (dt, 1H, JH‒H = 2, 8 Hz, Py),

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7.57 (t, 1H, JH‒H = 8 Hz, C6H4), 7.37—7.09 (m, 13H, Py, Ph, C6H4), 7.28 (1H, CH), 6.17 (d, 1H, JP‒H = 7 Hz, CH), 4.16 (br, 1H, NH) ppm. 13C{1H} NMR (CD2Cl2+CS2, 23 ºC): 171.3, 157.9, 154.6, 154.5, 154.4, 154.3, 154.2, 150.0, 147.7, 147.6, 147.5, 147.4, 146.8, 146.7, 146.6, 146.5, 145,4, 146.3, 146.2, 146.1, 146.0, 145.9,

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145.8, 145.7, 145.6, 145.4, 145.3, 145.0, 144.9, 144.8, 144.7, 144.6, 143.8, 143.6, 143.5, 143.4, 143.1, 143.0, 142.9, 142.7, 142.6, 142.5, 142.4, 142.3, 142.2, 142.1, 142.0, 139.9, 139.8, 139.7, 139.0, 138.5, 137.3, 137.2,

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134.8, 134.6, 133.7, 133.5, 133.0, 132.5, 132.4, 130.4, 130.3, 130.2, 129.5, 129.4, 129.2, 129.1, 129.0, 124.0, 123.8, 71.9, 60.8 ppm. 31P{1H} NMR (CD2Cl2, 25 ºC): ‒20.12 (s) ppm. HRMS (ESI) m/z Calc. for C85H21N2P: 1101.1440. Found: 1101.1448.

Reaction of 1 with Os3(CO)11(NCMe)

Compound 1 (100 mg, 0.09 mmol), Os3(CO)11(NCMe) (83 mg, 0.09 mmol), and toluene (50 ml) were placed in an oven-dried 100 ml Schlenk flask equipped with a condenser. The solution was heated to reflux for 10 min under dinitrogen. The solvent was removed under vacuum, and the residue was subjected to TLC, with

ACCEPTED CS2/CH2Cl2 (2:1, v/v) as eluent. Crystallization of theMANUSCRIPT material forming the major brown band from CS2/n-hexane produced air-stable, dark brown crystals of Os3(CO)11(η1-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (2; 69 mg, 0.035 mmol, 39%). IR (CH2Cl2, νCO): 2107m, 2055s, 2034m, 2018vs, 1998m, 1989m, 1976sh, 1959w cm‒1. 1H NMR (CD2Cl2, 25 ºC): 8.56—7.20 (m, 18H, Py, Ph, C6H4), 5.75 (s, 1H, CH), 5.14 (d, 1H, JP‒H

C96H21N2O11Os3P: 1983.9725. Found: 1983.9720.

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Reaction of 1 with W(CO)4(NCMe)2

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= 6 Hz, CH), 3.53 (br, 1H, NH) ppm. 31P{1H} NMR (CD2Cl2, 25 ºC): 0.02 (s) ppm. HRMS (ESI) m/z Calc. for

Compound 1 (100 mg, 0.09 mmol), W(CO)4(NCMe)2 (34 mg, 0.09 mmol), and dichloromethane (50 ml)

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were placed in an oven-dried 100 ml Schlenk flask. The solution was stirred at ambient temperature under dinitrogen for 18 h. The solvent was removed under vacuum, and the residue was subjected to TLC, with CS2/CH2Cl2 (2:1, v/v) as eluent. Isolation of the material forming the major brown band gave W(CO)4(η2-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (3; 85 mg, 0.06 mmol, 67%). IR (CH2Cl2, νCO): 2009s,

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1881vs, 1846s cm‒1. 1H NMR (CD2Cl2, 25 ºC): 8.48—6.96 (m, 18H, Py, Ph, C6H4), 6.65 (br, 1H, NH), 6.06 (br, 2H, CH) ppm. 31P{1H} NMR (CD2Cl2, 25 ºC): 28.87 (s, with 183W satellites, JW‒P = 225 Hz) ppm. HRMS (ESI)

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m/z Calc. for C89H21N2O4PW: 1396.0742. Found: 1396.0755.

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Reaction of 1 with Ru3(CO)12

Compound 1 (100 mg, 0.09 mmol), Ru3(CO)12 ( 57 mg, 0.09 mmol), and chlorobenzene ( 30 ml) were placed in an oven-dried 100 ml Schlenk flask. The solution was heated at 60 ºC for 7 h under a dinitrogen atmosphere. The solution was cooled to ambient temperature and filtered to remove black precipitates. The solvent was vaporized under vacuum, and the residue was subjected to TLC, with CS2/ethyl acetate (9:1, v/v) as eluent. Isolation of the material forming the major dark green band gave Ru(CO)3(η3-PPh2(o-C6H4)(o-C5H4N)(C2H3NC60)) (4; 51 mg, 0.04 mmol, 44%). IR (CH2Cl2, νCO): 2078s, 2005vs, 1983s cm‒1. 1H NMR (CD2Cl2, 25 ºC): 8.53 (d, 1H, JH‒H = 5 Hz, Py), 8.13 (m, 1H, C6H4), 7.77—7.09 (m, 16H, Py, Ph, C6H4), 6.72 (s, 1H, CH), 5.73 (d, 1H, JP‒H = 7 Hz, CH), 4.05 (br, 1H, NH) ppm. 31P{1H} NMR

2 ACCEPTED MANUSCRIPT (CD2Cl2, 25 ºC): 17.43 (s) ppm. 13C{1H} NMR (CD2Cl 2+CS2, 25 ºC): 75.6, 71.8 (η -C) ppm. HRMS (ESI)

m/z Calc. for C88H21N2O3PRu: 1286.0333. Found: 1286.0319.

Reaction of 4 with Ru3(CO)12

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Compound 4 (21 mg, 0.016 mmol), Ru3(CO)12 (10 mg, 0.016 mmol), and chlorobenzene ( 5 ml) were placed in an oven-dried 25 ml Schlenk flask equipped with a condenser. The solution was heated to reflux under a dinitrogen atmosphere for 10 min. The solvent was removed under vacuum, and the residue was

material forming the bright orange-yellow band afforded

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subjected to TLC, with CS2 as eluent. C60 (2.5 mg) was obtained from the first purple band. Isolation of the

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(µ-H)Ru4(CO)11(µ4,η4-PPh2(o-C6H4)CH2NC(o-C5H4N)) (5; 3 mg, 0.0027 mmol, 17%). IR (CH2Cl2, νCO): 2068m, 2037s, 2024vs, 1991m, 1980m, 1952w cm‒1. 1H NMR (CD2Cl2, 25 ºC): 7.92—6.92 (m, 17H), 6.31 (t, 1H, JH‒H = 7 Hz), 4.03 (d, 1H, JH‒H = 12 Hz, CH2), 3.71 (m, 1H, CH2), ‒17.48 (s, 1H, µ-H) ppm. 31P{1H} NMR

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(CD2Cl2, 25 ºC): 27.42 (s) ppm. HRMS (ESI) m/z Calc. for C36H21N2O11PRu4: 1095.7057. Found: 1095.7077.

Structure determination for 1 and 5

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The crystals of 1 and 5 suitable for X-ray analysis were each mounted in a thin-walled glass capillary and aligned on the Nonius Kappa CCD diffractometer, with graphite-monochromated Mo Kα radiation (λ =

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0.71073 Å). The θ range for data collection is 2.55 to 25.09° for 1, and 1.25 to 25.13° for 5. Of the 40443 and 52646 reflections collected, 10688 and 13205 reflections were independent for 1 and 5, respectively. All data were corrected for Lorentz and polarization effects and for the effects of absorption. The structures were solved by the direct method and refined by least-square cycles. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included but not refined. All calculations were performed using the SHELXTL-97 package. The data collection and refinement parameters are presented in Table 1.

Acknowledgments

This work was financially supported by the Ministry of Science and Technology of Taiwan. We thank Mr. ACCEPTED MANUSCRIPT Ting-Shen Kuo (National Taiwan Normal University, Taipei) for X-ray diffraction analysis. Appendix A. Supplementary material CCDC 1489518 (1) and 1489519 (5) contain the supplementary crystallographic data for this paper.

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These data can be obtained free of charge from The Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif.

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[26] M. Maggini, G. Scorrano, M. Prato, J. Am. Chem. Soc. 115 (1993) 9798–9799.

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[27] R.H. Crabtree, The Organometallic Chemistry of the Transition Metals, Wiley, Hoboken, USA, 2009. [28] C.-C. Yang, W.-Y. Yeh, G.-H. Lee, S.-M. Peng, J. Organomet. Chem. 598 (2000) 353‒358. [29] S.-J. Wang, W.-Y. Yeh, Organometallics 31 (2012) 6491–6494.

[30] A.L. Balch, J.W. Lee, B.C. Noll, M.M. Olmstead, Inorg. Chem. 32 (1993) 3577‒3578.

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[31] M. Rasinkangas, T.T. Pakkanen, T.A. Pakkanen, J. Organomet. Chem. 476 (1994) C6‒C8. [32] H. Kang, B.K. Park, Md.A. Miah, H. Song, D.G. Churchill, S. Park, M.-G. Choi, J.T. Park, J. Organomet. Chem. 690 (2005) 4704‒4711.

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[33] H. Fischer, S. Zeuner, J. Organomet. Chem. 327 (1987) 63‒75. [34] D. Braga, F. Grepioni, E. Parisini, B.F.G. Johnson, C.M. Martin, J.G.M. Nairn, J. Lewis, M. Martinelli, J.

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Chem. Soc. Dalton Trans. (1993) 1891‒1895.

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Table 1

Crystallographic data for 1 and 5. _____________________________________________________________________ 1 5 _______________________________________________________ C85H21N2P

C36H20N2O11PRu4

T (K)

200(2)

200(2) K

Crystal system

Monoclinic

Monoclinic

Space group

C2/c

P21/n

a (Å)

25.261(9)

19.7331(8)

b (Å)

25.918(12)

19.3690(8)

c (Å)

19.737(8)

α (°)

90

β (°)

110.273(13)

γ (°)

90

20.4704(8)

90

107.922(2)

90

12122(9)

7444.3(5)

Z

8

8

Dcalc (g cm–3)

1.207

wR2

(all data)

EP

Goodness-of-fit on F2

1.948

4480

4232

0.095

1.697

AC C

µ (mm–1) R1 (I > 2σ(I))

TE D

V (Å3)

F(000)

SC

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Unit cell dimensions

RI PT

Formula

0.0953

0.0327

0.2855

0.1144

0.861

1.126

__________________________________________________

ACCEPTED MANUSCRIPT

Equations 1~5 O NH2

+

H

H N

N

O 2 H

N

PPh2

C

Ph H

H

P

0 6

C

Ph

H N

N

(1) C H

C H

syn

PPh2

1

H N H

H

1

(CO)4

Os

Ph P

Os (CO)3

Ph

+ Os3(CO)11(NCMe)

(CO)4

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2

O C

OC

O C

OC

RT N

N

P

H

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+ W(CO)4(NCMe)2

H

H

Ph

Ph

W

1

AC C

N

1

(2)

Os

SC

N

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H2 C

H

(3)

3

H N H

P

+ Ru3(CO)12

Ph Ph

Ru (CO)3

(4)

4

H N

N

H

H

N

Ru(CO)3 + Ru3(CO)12

C

P

Ru (CO)2 N

Ru (CO)3

H

4

Ph

Ph

Ph P Ph

Ru (CO)3

+

CH2

Ru (CO)3

5

C60

(5)

ACCEPTED Fig. 1. Molecular structure of 1 with 30% probabilityMANUSCRIPT ellipsoids. Selected bond distances (Å) and bond angles (º): C13–C18 1.407(7), C18–C19 1.494(7), C19–C27 1.573(7), C20–C21 1.518(7), C20–C26 1.574(6), C26–C27 1.607(6), N1–C19 1.461(6), N1–C20 1.441(6), C1–P1 1.823(5), C7–P1 1.797(7), C13–P1 1.816(6) and C1–P1–C7 101.2(3), C1–P1–C13 104.6(3), P1–C13–C18 121.5(4), C13–C18–C19 123.2(5),

EP

TE D

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SC

N1–C20–C26 102.1(4), C20–C26–27 103.3(4), C19–C27–C26 102.6(3).

RI PT

C18–C19–N1 112.0(4), C18–C19–C27 117.3(4), C19–N1–C20 105.7(4), N1–C20–C21 113.7(5),

AC C

Fig. 2. 300 MHz 1H NMR spectra of 1 in CD2Cl2 at 25 ºC.

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Fig. 4. Proposed configurations for 3 and 4.

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SC

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ACCEPTED Fig.3. 300 MHz 1H NMR spectra for compounds 2–5MANUSCRIPT obtained in CD2Cl2 at 25 ºC.

ACCEPTED Fig. 5. Molecular structure of 5 with 30% probabilityMANUSCRIPT ellipsoids. Selected bond distances (Å) and bond angles (º): Ru1–Ru2 2.8102(7), Ru2–Ru3 2.7859(7), Ru2–Ru4 2.9600(6), Ru3–Ru4 2.7464(6), P1–Ru1 2.3518(15), N1–Ru1 2.156(4), N1–Ru4 2.152(4), N2–Ru1 2.148(5), C42–Ru2 2.197(6), C42–Ru3 2.078(6), C41–N1 1.485(7), C42–N1 1.457(7) and Ru1–Ru2–Ru3 107.77(2), Ru1–Ru2–Ru4 78.807(17), Ru3–Ru2–Ru4 57.010(15), Ru2–Ru3–Ru4 64.689(17), Ru2–Ru4–Ru3 58.301(16), P1–Ru1–Ru2 159.64(4), P1–Ru1–N1

RI PT

91.85(12), P1–Ru1–N2 94.30(13), Ru1–P1–C35 107.15(19), Ru1–N1–Ru4 116.6(2), Ru2–C42–Ru3 81.3(2), C40–C41–N1 111.4(4), C41–N1–C42 115.9(4), N1–C42–C43 108.9(5), N1–C42–Ru2 100.5(3),

AC C

EP

TE D

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SC

N1–C42–Ru3 117.0(3).

ACCEPTED MANUSCRIPT

Captions to the figures

Fig. 1. Molecular structure of 1 with 30% probability ellipsoids. Selected bond distances (Å) and bond angles (º): C13–C18 1.407(7), C18–C19 1.494(7), C19–C27 1.573(7), C20–C21 1.518(7), C20–C26 1.574(6), C26–C27 1.607(6), N1–C19 1.461(6), N1–C20 1.441(6), C1–P1 1.823(5), C7–P1 1.797(7), C13–P1 1.816(6) and C1–P1–C7 101.2(3), C1–P1–C13 104.6(3), P1–C13–C18 121.5(4), C13–C18–C19 123.2(5), C18–C19–N1 112.0(4), C18–C19–C27 117.3(4), C19–N1–C20 105.7(4), N1–C20–C21 113.7(5),

Fig. 2. 300 MHz 1H NMR spectra of 1 in CD2Cl2 at 25 ºC.

RI PT

N1–C20–C26 102.1(4), C20–C26–27 103.3(4), C19–C27–C26 102.6(3)

SC

Fig.3. 300 MHz 1H NMR spectra for compounds 2–5 obtained in CD2Cl2 at 25 ºC. Fig. 4. Proposed configurations for 3 and 4.

M AN U

Fig. 5. Molecular structure of 5 with 30% probability ellipsoids. Selected bond distances (Å) and bond angles (º): Ru1–Ru2 2.8102(7), Ru2–Ru3 2.7859(7), Ru2–Ru4 2.9600(6), Ru3–Ru4 2.7464(6), P1–Ru1 2.3518(15), N1–Ru1 2.156(4), N1–Ru4 2.152(4), N2–Ru1 2.148(5), C42–Ru2 2.197(6), C42–Ru3 2.078(6), C41–N1 1.485(7), C42–N1 1.457(7) and Ru1–Ru2–Ru3 107.77(2), Ru1–Ru2–Ru4 78.807(17), Ru3–Ru2–Ru4 57.010(15), Ru2–Ru3–Ru4 64.689(17), Ru2–Ru4–Ru3 58.301(16), P1–Ru1–Ru2 159.64(4), P1–Ru1–N1

AC C

EP

TE D

91.85(12), P1–Ru1–N2 94.30(13), Ru1–P1–C35 107.15(19), Ru1–N1–Ru4 116.6(2), Ru2–C42–Ru3 81.3(2), C40–C41–N1 111.4(4), C41–N1–C42 115.9(4), N1–C42–C43 108.9(5), N1–C42–Ru2 100.5(3), N1–C42–Ru3 117.0(3).

ACCEPTED MANUSCRIPT Highlights:

(1) PPh2(o-C6H4)(o-C5H4N)(C2H3NC60) was prepared and structurally characterized. (2) PPh2(o-C6H4)(o-C5H4N)(C2H3NC60) reveals versatile bonding modes with metal complexes.

AC C

EP

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SC

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(3) The fullerene addend can be transferred to a tetraruthenium cluster.