有機金屬化合物在有機合成與材料的應用(2/3)

行政院國家科學委員會專題研究計畫 期中進度報告

有機金屬化合物在有機合成與材料的應用(2/3)

期中進度報告(精簡版)

計 畫 類 別 ： 個別型 計 畫 編 號 ： NSC 95-2119-M-002-008- 執 行 期 間 ： 95 年 08 月 01 日至 96 年 11 月 30 日 執 行 單 位 ： 國立臺灣大學化學系暨研究所 計 畫 主 持 人 ： 林英智 報 告 附 件 ： 出席國際會議研究心得報告及發表論文 處 理 方 式 ： 本計畫可公開查詢

中 華 民 國 96 年 12 月 10 日

行政院國家科學委員會補助專題研究計畫

□ 成 果 報 告

■期中進度報告

（計畫名稱）

有機金屬化合物在有機合成與材料的應用(2/3)

計畫類別：■ 個別型計畫

□ 整合型計畫

計畫編號：NSC 95－2119－M－002－008－

執行期間：

95 年 8 月 1 日至 96 年 11 月 1 日

計畫主持人：林英智

共同主持人：

計畫參與人員：

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□完整報告

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執行單位：國立臺灣大學化學系暨研究所

中

華

民

國

96

年

5

月

4

日

附件一

有機金屬化合物在有機合成與材料的應用

Abstract: This is a brief report including three parts: 1. Chemistry of ruthenium vinylidene complexes. 2. Photoluminescence of alkynyl complexes. 3. Chemistry of Iron vinylidene complexes. The new metathesis of the terminal vinyl group with the C=C of the vinylidene group is confirmed by13C labeling studies. A number of star-shaped molecules with silyl group and an aromatic core surrounded by extended π conjugativearms has been synthesized by using Sonogashira coupling methods and show excellent fluorescence intensity with high quantum yield. Finally Two iron complexes each containing 1-ferra-2,5-diphospha-[2.1.1] ring are prepared by deprotonation reaction of cationic vinylidene complexes [Fe]=C=C(Ph)CH2R+ ([Fe] = (η5

-C5H5)(dppe)Fe, R = CH=CH2, and Ph).

Keyword: ruthenium, vinylidene, photoluminescence, iron, alkynyl

I. Chemistry of ruthenium vinylidene complexes.

The cationic complex {[Ru]=C=CHCPh2CH2CH=CH2}BF4 (3a, [Ru] = (η5-C5H5) (PPh3)2Ru) in solution transforms to {[Ru]=C=CHCH2CPh2CH=CH2}BF4(4a) via a new metathesis process of the terminal vinyl group with the C=C of the vinylidene group which is confirmed by 13C labeling studies. This transformation is irreversible as revealed by deuteration and decomplexation studies. The cationic complex {[Ru]=C=CHCPh2CH2CMe=CH2}BF4 (3b) undergoes a cyclization process yielding 6b containing a η2-cyclic allene ligand which is fully characterized by single crystal X-ray diffraction analysis. Analogous complexes 4a’and 6b’ ([Ru] = (η5-C5H5) (dppe)Ru) containing dppe ligands were similarly obtained from protonation of the corresponding acetylide complexes via formation of vinylidene intermediate. Protonation of the acetylide complex containing a terminal alkynyl group [Ru]- C≡CCPh2CH2C≡CH (2c) generates the vinylidene complex {[Ru]=C=CH- CPh2CH2C≡CH}BF4 (3c) which again undergoes an irreversible transformation to give {[Ru]=C=CHCH2CPh2C≡CH}BF4(4c) possibly via a π-coordinated alkynyl complex followed by hydrogen and metal migration. No similar transformation is observed for the analogous dppe complex 3c’. With an extra methylene group, complex {[Ru]=C=CHCPh2CH2CH2CH=CH2}BF4 (3d), as well as {[Ru]=C= CHCPh2CH2Ph}BF4 (3e), are stable. Presence of a gem-diphenylmethylene moiety at the vinylidene ligand with appropriate terminal vinyl or alkynyl group along with correct steric environment implement such a novel reactivity in the ruthenium vinylidene complexes.

[Ru] C [Ru] Ph Ph C [Ru] Ph Ph Ph Ph 3a 4a 5a HC C Ph Ph CH3CN CH3CN   7a only 8a HC C _Ph Ph 8a [Ru] CH3CN + + [Ru] CH3CN +

A series of star-shaped molecules with silyl group and an aromatic core surrounded by extended π conjugativearms has been synthesized by using Sonogashira coupling methods and show excellent fluorescence intensity with high quantum yield. These molecules undergo desilylation in the presence of n-Bu4NF to give terminal polyalkynyl compounds. By incorporating metal moieties such as palladium, platinum and gold into these compounds, star-shaped molecules can be obtained. Photophysical properties of these molecules are investigated spectroscopically in solution. These star-shaped molecules are characterized by IR, NMR (1H,31P and13C) spectroscopy, as well as MALDI-TOF mass spectrometry.

III. Chemistry of Iron vinylidene complexes.

Two iron complexes each containing 1-ferra-2,5-diphospha-[2.1.1] ring are prepared by deprotonation reaction of cationic vinylidene complexes [Fe]=C=C(Ph)CH2R+ ([Fe] = (η5

-C5H5)(dppe)Fe, R = CH=CH2, and Ph). The deprotonation takes place at the methylene proton of the dppe ligand which is followed by an intramolecular addition giving the product. For similar vinylidene complexes with R = CN, p-C6H4CN and p-C6H4CF3, the deprotonation reaction gave the cyclopropenyl complexes. The deprotonation of the vinylidene complex with R = C6F5 gave both the cyclopropenyl complex and the product containing a 1-ferra-2,5-diphospha-[2.1.1] ring system. The electron- withdrawing ability of substituent near the Cγ-methylene group of the vinylidene ligand determines the selectivity of deprotonation. Characterizations of vinylidene, cyclopropenyl complexes and a complex containing a 1-ferra-2,5- diphospha-[2.1.1] ring are carried out using single crystal X-ray diffraction analysis.

CH2Cl2, reflux [Fe] C C [Fe] C C R RCH2X 3 [Fe] R H Fe Ph2P PPh2 base [Fe] = Ph Ph Ph Fe Ph2P_Ph 2P Ph R 5a, R = CN, 5b, R = C6H4CN, 5c, R = C6H4CF3 6d, R = CH=CH2, 6e, R = C6H5, 6f, R = C6F5 base 4a, R = CN, 4b, R = C6H4CN, 4c, R = C6H4CF3 4d, R = CH=CH2, 4e, R = C6H5, 4f, R = C6F5

References are cited in the following articles:

1. Yung-Sheng Yen, Ying-Chih Lin,* Shou-Ling Huang, Yi-Hung Liu, Hui-Ling Sung, and Yu Wang (2005) Intramolecular Metathesis of a Vinyl Group with Vinylidene C=C Double Bond in Ru Complexes J. Am. Chem. Soc. 2005, 127, 18037-18045.

2. Ku-Hsien Chang, Hui-Ling Sung, and Ying-Chih Lin* (2006) Reactions of Furylruthenium

Complexes with Oxygen and Trimethylsilyl AzideEur. J. Inorg. Chem. 2006, 649 –655.

3.Chiung-Cheng Huang, Ying-Chih Lin,* Ping-Yu Lin, and Yu-Ju Chen(2006)Star-Shaped

Molecules Containing Polyalkynyl Groups with Metal Moieties on Benzene and Triphenylene

Cores.Eur. J. Org. Chem. 2006, 4510–4518.

4.Hung-Chih Lin, Chiung-Cheng Huang, Chih-Hau Shi, Yong-Hong Liao, Chien-Chih Chen, Ying-Chih Lin* and Yi-Hong Liu(2007),Synthesis of alkynylated photo-luminescent Zn(II) and Mg(II) Schiff base complexes.Dalton Trans. 2007, 781- 791.

Vinylidene Complexes Containing dppe Ligand Organometallics 2007, 26, 1250 - 1255.

出席國際學術會議心得報告

會議名稱:

The 17

th

International Symposium on Olefin Metathesis (ISOM 17)

地點:

Hilton Hotel Pasadena California U.S.A.

時間:

July 28-Aug 03 2007

林英智

台大化學系教授

The 17thInternational Symposium on Olefin Metathesis (ISOM 17) was held at Pasadena California on July 28-Aug 03 2007. The symposium was held in the Hilton Hotel Pasadena, a nice meeting place near the campus of Caltech. A small business

company Materia was set up by a very successful research result of Prof. Grubbs. Materia is a small company with about 60 people focus mainly on applying the result

of research activity in California Institute of Technology in business. The major product of the company is derived from the polymerization of DCPD (dicyclopentadienide) using Grubbs’catalyst. Because of easy fabrication of the

process, the product could be easily molded into some specific shape.

There are about 200 attendees including many chemists from Europe and Japan. The six days schedule is filled with oral presentations and two poster sessions. Many reports involve application of olefin metathesis in the organic synthesis particularly formation of macrocyclic ring in natural products and preparation of polymers. A few report even used the concept of metathesis to fix the conformation of biological molecules.

In the introduction session Professor Robert H Grubbs stressed that olefin

metathesis is being recognized as a green chemistry. The reaction not only increases the efficiency in terms of synthetic steps and the lack of contaminating by-products but it also open new routes for the conversion of biomaterial into useful products. Products in which petroleum-based starting materials are being replaced by renewable sources are now starting to reach the market. A wide range of ruthenium-based alkylidene complexes is now commercially available and applications are now starting to become a commercial reality.

Professor Dixneuf, Pierre reported the transition-metal-catalyzed organic

transformation of alkynes involving vinylidene intermediates. Vinylidene complexes, which can be mono-, di-, or polynuclear, are known for most transition metals and may be prepared by a variety of methods. The most pertinent route to mononuclear vinylidenes involves the reaction of an alkyne with a transition-metal substrate. The alkynes can be terminal or internal with alkyl/aryl/silyl substituents. Although the chemistry of (vinylidene)metal complexes has been extensively investigated, mononuclear bis(vinylidene) complexes remain unknown. A mononuclear

bis(vinylidene) species was proposed as a reactive intermediate in the formation of tetrakis(trimethylsilyl)butatriene. They have isolated an unprecedented ruthenium bis(vinylidene) complex from the reaction of [ 5: -Me2C(C5H4)(C2B10H10

)]Ru-(NCCH3)2with silylalkyne.

The keynote speaker Hoveyda of the Boston College reported the synthesis, characterization, and reactivities of molybdenum bispyrrolyl complexes of the type Mo(NR)(CHR')(pyrrolyl)2where pyrrolyl is either the parent pyrrolyl or

2,5-dimethylpyrrolyl (Me2Pyr) in the use of bispyrrolyl species as precursors to bisalkoxide catalysts of the type Mo(NR)(CHR')(OR)2or Mo(NR)(CHR')(diolate) through addition of an alcohol or a diol to Mo(NR)(CHR')(pyrrolyl)2complexes. Preliminary experiments suggest that bispyrrolyls are less reactive toward olefins than bisalkoxide species, but serve as effective precursors to Mo-based bisalkoxides or diolates. The high reactivities are observed for supported catalysts prepared through addition of bispyrrolyl species to silica where the predominant surface species is Mo(NR)(CHR')(pyrrolyl)(OSisurf). High catalytic activities have been observed (and also rationalized through theoretical studies) for these and related pseudotetrahedral metal complexes that are asymmetric at the metal center. The synthesis of species of the type Mo(NR)(CHR')(OR' ')(pyrrolyl) and their use in catalytic enyne metathesis reactions are reported.

I submitted a poster with the title “Intramolecular Cyclization of Ruthenium Vinylidene Complexes with a Tethering Vinyl Group: Facile Cleavage and

Reconstruction of C-C Double Bond”. It was good to talk with top-notched scientist for research results at the poster session and obtained some valuable suggestions from them. I got the chance to chat with Professor Grubbs and Professor Dixneuf and had a nice exchange of research idea with them. The paper is just accepted by the

Intramolecular Cyclization of Ruthenium Vinylidene Complexes with a Tethering Vinyl Group: Facile Cleavage and Reconstruction of C-C

Double Bond

Cheng-Wei Cheng, Yi-Chun Kuo, Shu-Hao Chang, Ying-Chih Lin*

Department of Chemistry, National Taiwan University Taipei, Taiwan 106 E-mail:yclin@ntu.edu.twFAX: 886-2-23636359

Protonation of [M]-*C≡*CCPh2CH2CH=CH2(2a,[M]= [Ru]= (η 5

-C5H5)(P(OPh)3)(PPh3)Ru;2a’,

[M] = [Ru’] = (η5

-C5H5)(dppp)Ru; *C = 13

C labeled carbon atom) with HBF4 produces

{[M]=*C=CHCH2CPh2*CH=CH2}[BF4] (4, 4’) exclusively via a metathesis process of the

terminal vinyl group with the *C=*C of the vinylidene group. For 4 in methanol, bond reconstruction of the two labeled *C atoms readily takes place via a retro-metathesis process followed by a cyclization of the resulting vinylidene ligand giving the cyclic carbene complex 5. The protonation of 2a in MeOH is followed by a cyclization also giving 5. Duteurium-labeling study indicated that the C-C bond formation of this cyclization proceeds simultaneously with the formation of 4 consistent with facile cleavage and reconstruction of C=C bonds. For comparison, complex 4 iniPrOH yields, besides 5, the corresponding alkoxycyclohexene 6c. Formation of 6c from 4 also involved a skeletal rearrangement with reconstruction of the C=C bond.Interestingly {[Ru’]=*C=C(Me)CH2CPh2*CH=CH2}[BF4] (8’) originally from complex with

two connected labeled carbon atoms also undergoes reestablishment of the *C=*C bond yielding the cyclic allene complex9’.13C labeling studies clearly reveal the reestablishment of the C=C double bond both in the transformation of 4 to 5 and 8’to 9’. The proposed mechanism implicates a cyclobutylidene intermediate formed via either a regiospecific [2+2] cycloaddition of two double bonds in the ruthenium-vinylidene 4, or via a 5-endo cyclization of

4 giving a nonclassical ion intermediate followed by a 1,2-alkyl shift.

HBF4 HBF4 2 2' + 5 Ph Ph OR * * 6a, R = Me 6c, R =iPr 6b, R = Et 6d, R = H 5 C [Ru] Ph Ph * * [M] C C Ph Ph 2a, 2a' * * [Ru] C C H C3 C4 Ph Ph 3a' * * [Ru] C C H C3 C4 PhPh 4, 4' * *

n, [M] = [Ru] = Cp(P(OPh)3)(PPh3)Ru n', [M] = [Ru'] = Cp(dppp)Ru

MeOH

4

4

References:

(1) Luzung, M. R.; Markham, J. P.; Toste, F. D. J. Am. Chem. Soc. 2004, 126, 10858.

(2) Nieto-Oberhuber, C.; Muñoz, M. P.; Buñuel, E.; Nevado, C.; Cárdenas, D. J.; Echavarren, A. M. Angew. Chem., Int. Ed. 2004, 43, 2402.

(3) Yen, Y. S.; Lin, Y. C.; Huang, S. L.; Liu, Y. H.; Sung, H. L.; Wang, Y. J. Am. Chem. Soc. 2005, 127, 18037.