4-1 總結
將目前所知的 [Cu(TMSPS3)(X)]0/− 錯合物生成和衍生機制，統整 如下圖 4-1。三價銅錯合物製備時，添加的的氯離子會和 CuCl2結合 形成 [Cu2Cl6]2− 二聚體並溶於 CH3CN。二聚體與 TMSPS33− 結合時，
配位基的負電場驅使二價銅進行自身氧化還原，產生三價的錯合物 1 和 [CuCl2]− 亞銅副產物；氧氣可協助亞銅副產物的回收，使之氧化 並再次參與錯合反應。而 [Cu(TMSPS3)(X)]0/− 錯合物種在溶液中實為 動態平衡，錯合物 1 的軸位氯離子能夠輕易地與其他的配基進行交換 (雖然也是影響錯合產率的主因)，如此三角雙錐三價銅系統，是前所 未見的。據此，我們可由錯合物 1 衍生製備不同的三角雙錐三價銅錯
圖 4-1 統整 [Cu(TMSPS3)(X)]0/− 錯合物的形成與衍生化。
合物，如錯合物 2–4。129此外，錯合物 1 與 OH− 在 CH3CN 溶劑中，
可能經由某種高活性的 CuIII–OH 物種，促使 CH3CN 發生 C–CN 鍵的 斷裂及錯合物 5 的形成。在低溫的條件下，藉由 Sc(OTf)3移除錯合物 1 的軸位軸位配基，使 Cu(TMSPS3) 片段呈現近乎四配位的狀態，隨 溫度回升而進行二聚化反應，生成三價銅二聚物 6。
4-2 未來展望
和數種溫和的 hydride 試劑 (NaBH4、NaBH(OAc)3等) 進行反應，128 雖還未分離出穩定的產物，但有機會作為 hydride 的轉移、活化媒介。
最近更發現，錯合物 1 和 NaBH3CN 在低溫 THF 中可形成穩定的 1:1 複合物，而最新單晶繞射解析為 [PPN][CuIII(TMSPS3)(NCBH3)]，其中 BH3CN− 陰離子以 cyano 基團的氮原子配位於 Cu(TMSPS3) 基團且將 BH3基團朝向分子外側。128此錯合物在 0 °C 以上則緩緩變質，應仍 有 hydride 的活性，只待尋找合適的反應/催化條件。
圖 4-2 [NiIII(TMSPS3)(H)]− 物種的形成與反應。93g
某些置換反應中，如錯合物 1 和 PPh3作用，Cu(TMSPS3) 配位系 統的特徵吸收峰會逐漸消失，疑似三價銅經兩個電子的還原轉變成一 價銅物種 (須先排除二聚化導致的錯合物析出，參閱 3-6 節)。以 DFT 計算 CuIII–OtBu、CuIII–PPh3還原的可能產物，由所得結構的相對位能 (圖 4-3) 可知：CuIII–OtBu 沒有異構化的驅勢 (ΔE ≈ +3 kcal/mol)；而 CuIII–PPh3 顯然趨向 (disulfide-TMSPS3)CuI–PPh3 之異構產物 (ΔE ≈
−116 kcal/mol)，代表 CuIII–X 發生分子內的氧化還原不無可能。
Cu(TMSPS3) 基團可能因軸位配基的電子效應，促發分子內 bisthiolate–
disulfide 的氧化還原。從另一個角度說，Cu(TMSPS3) 配位系統可以有 兩個電子儲存於 thiolate 形式。能否運用此效應於催化劑的開發，也 是值得探究的議題。
4-2.2 三價銅之催化反應開發
近十年來，陸續有文獻報導以碳烯 (carbene) 配位的一價銅催化 劑，如 [IPrCu(OtBu)]，可搭配硼烷催化數種不同型態的反應，130–134 包括：二氧化碳還原為一氧化碳、130 硼基化 (borylation) 反應、131 硼基苯加成 CO2之羧基化 (carboxylation) 反應、132不飽和鍵之硼氫 化 (hydroborylation)132b,133 反應等，展現出銅—硼—氧之間獨特的化 學多樣性。目前公認的機構列舉如圖 4-4 及 4-5，這些催化反應共通 之關鍵是：硼—氧化學鍵生成之驅動力、以及 [(IPr)Cu(Bpin)] 銅—
硼中間體之形成。
圖 4-4 鹵苯硼基化反應可能的催化機構。131
圖 4-5 有機硼酯的羧基化反應可能的催化機構。132a
以理論計算 [(IPr)Cu(Bpin)] 中間體的 Mulliken 電荷，Cu/B 原子 為 +0.48/−0.59；另假設本研究配位系統之 [Cu(TMSPS3)(Bpin)]− 物種，
則 Cu/B 原子的 Mulliken 電荷為 +0.52/−0.59。雖然形式電荷相差兩 個氧化態，由於TMSPS33− 配位基的電子補償效應，[Cu(TMSPS3)(Bpin)]− 和 [(IPr)Cu(Bpin)] 兩者的有效電荷其實相去不遠。此外，三價鎳 [NiIII(TMSPS3)(OPh)]− 和 HBpin 的反應性93g 亦支持 [Cu(TMSPS3)(X)]0/−
系統可能進行類似的反應。
最近 Z. Shen 等人報導以 Cu(OAc)2搭配 TEMPO 催化硼基苯的氰 化反應，135其中氰根離子是源自 CH3CN 溶劑，如此可避免傳統方法 使用之毒性反應試劑 (如 NaCN、TMSCN、K4[Fe(CN)6] 等)。根據他 們所推論的機構，參考圖 4-6 所示，銅離子在其催化反應中扮演了雙 重角色：一、銅一/三價氧化加成—還原脫去之 aryl–CN 鍵耦合循環 (圖 4-6 Cycle C)；二、與氧氣進行 SET 促發 CH3CN 之 HAT 反應 (圖
圖 4-6 推測之 Cu(OAc)2/TEMPO 催化硼基苯氰化反應機制。135
4-6 Path A &B)，生成 TEMPO–CH2CN 物種作為 CN− 離子的前驅物。
其中的中間體 TEMPO–CH2CN，是由產物之條件分析和 GC 佐證。此 與錯合物 5 的形成過程 (參閱 3-5 節討論)，似乎有異曲同工之妙。假 使能提供妥善的條件及適合的反應物，或許目前觀察到的 CH3CN 裂 解，不失為是潛在的氰化反應試劑。
前面提及的各種催化方法，大多仍仰賴搜索金屬前驅物、添加配 位基及輔助試劑的排列組合。假使運用本研究奠定的配位基設計與化 學勢資訊，或可對新型態之高價銅催化反應開發有所突破。
參考文獻
1. David L. Nelson, Michael. M. Cox Lehninger Principles of Biochemistry, 6/ed;
W. H. Freeman & Company: New York, 2012; pp 158–172.
2. John. T. Groves, Robert C. Haushalter, Mikio Nakamura, Thomas E. Nemo, B. J.
Evans J. Am. Chem. Soc. 1981, 103, 2884–2886.
3. James E. Penner-Hahn, Kim Smith Eble, Thomas J. McMurry, Mark Renner, Alan L. Balch, John T. Groves, John H. Dawson, Keith O. Hodgson J. Am.
Chem. Soc. 1986, 108, 7819–7825.
4. (a) Hans-Petter Hersleth, Ulf Ryde, Patrik Rydberg, Carl Henrik Görbitz, K.
Kristoffer Andersson J. Inorg. Biochem. 2006, 100, 460–476. (b) Jonathan Rittle, Michael T. Green Science 2003, 299, 1037–1039.
5. Johannes Hohenberger, Kallol Ray, Karsten Meyer Nat. Commun. 2012, 3, No.
720.
6. Craig A. Grapperhaus, Bernd Mienert, Eckhard Bill, Thomas Weyhermüller, Karl Wieghardt Inorg. Chem. 2000, 39, 5306–5317.
7. Jan-Uwe Rohde, Jun-Hee In, Mi Hee Lim, William W. Brennessel, Michael R.
Bukowski, Audria Stubna, Eckard Münck, Wonwoo Nam, Lawrence Que Jr.
Science 2003, 299, 1037–1039.
8. Aidan R. McDonald, Lawrence Que Jr. Coord. Chem. Rev. 2013, 257, 414–428.
9. (a) Jason England, Marlène Martinho, Erik R. Farquhar, Jonathan R. Frisch, Emile L. Bominaar, Eckard Münck, Lawrence Que, Jr. Angew. Chem., Int. Ed.
2009, 48, 3622–3626. (b) Jason England, Yisong Guo, Erik R. Farquhar, Victor G. Young Jr., Eckard Münck, Lawrence Que Jr. J. Am. Chem. Soc. 2010, 132,
10. David C. Lacy, Rupal Gupta, Kari L. Stone, John Greaves, Joseph W. Ziller, Michael P. Hendrich, A. S. Borovik J. Am. Chem. Soc. 2010, 132, 12188–12190.
11. (a) József Kaizer, Eric J. Klinker, Na Young Oh, Jan-Uwe Rohde, Woon Ju Song, Audria Stubna, Jinheung Kim, Eckard Münck, Wonwoo Nam, Lawrence Que, Jr.
J. Am. Chem. Soc. 2004, 126, 472–473. (b) Eric J. Klinker, József Kaizer,
William W. Brennessel, Nathaniel L. Woodrum, Christopher J. Cramer, Lawrence Que, Jr. Angew. Chem., Int. Ed. 2005, 44, 3690–3694.
12. Mi Sook Seo, Nam Hee Kim, Kyung-Bin Cho, Jeong Eun So, Seon Kyung Park, Martin Clémancey, Ricardo Garcia-Serres, Jean-Marc Latour, Sason Shaik, Wonwoo Nam Chem. Sci. 2011, 2, 1039–1045.
13. Genqiang Xue, Raymond De Hont, Eckard Münck, Lawrence Que Jr Nat. Chem.
2010, 257, 400–405.
14. Debasish Mandal, Rajeev Ramanan, Dandamudi Usharani, Deepa Janardanan, Binju Wang, Sason Shaik J. Am. Chem. Soc. 2015, 137, 722–733.
15. Sarmistha Chakrabarty, Rachel N. Austin, Dayi Deng, John T. Groves, John D.
Lipscomb J. Am. Chem. Soc. 2007, 129, 3514–3515.
16. (a) Irene Prat, Jennifer S. Mathieson, Mireia Güell, Xavi Ribas, Josep M. Luis, Leroy Cronin, Miquel Costas Nat. Chem. 2011, 3, 788–793. (b) Aidan R.
McDonald, Lawrence Que, Jr. Nat. Chem. 2011, 3, 761–762.
17. (a) Filipe Tiago de Oliveira, Arani Chanda, Deboshri Banerjee, Xiaopeng Shan, Sujit Mondal, Lawrence Que Jr., Emile L. Bominaar, Eckard Münck, Terrence J.
Collins Science 2007, 315, 835–838. (b) Soumen Kundu, Jasper Van Kirk Thompson, Longzhu Q. Shen, Matthew R. Mills, Emile L. Bominaar, Alexander D. Ryabov, Terrence J. Collins Chem.—Eur. J. 2015, 21, 1803–1810.
18. Munmun Ghosh, Kundan K. Singh, Chakadola Panda, Andrew Weitz, Michael P.
Hendrich, Terrence J. Collins, Basab B. Dhar, Sayam Sen Gupta J. Am. Chem.
Soc. 2014, 136, 9524–9527.
19. W. Chadwick Ellis, Neal D. McDaniel, Stefan Bernhard, Terrence J. Collins J.
Am. Chem. Soc. 2010, 132, 10990–10991.
20. (a) Chakadola Panda, Joyashish Debgupta, David Dí az Díaz, Kundan K. Singh, Sayam Sen Gupta, Basab B. Dhar J. Am. Chem. Soc. 2014, 136, 12273–12282.
(b) Zoel Codolà , Laura Gómez, Scott T. Kleespies, Lawrence Que, Jr., Miquel Costas, Julio Lloret-Fillol Nat. Commun. 2015, 6, No. 5865.
21. Edward I. Solomon, David E. Heppner, Esther M. Johnston, Jake W. Ginsbach, Jordi Cirera, Munzarin Qayyum, Matthew T. Kieber-Emmons, Christian H.
Kjaergaard, Ryan G. Hadt, Li Tian Chem. Rev. 2014, 114, 3659–3853.
22. (a) Edward I. Solomon, Uma M. Sundaram, Timothy E. Machonkin Chem. Rev.
1996, 96, 2563–2605. (b) Malte Rolff, Julia Schottenheim, Heinz Decker, Felix
Tuczek Chem. Soc. Rev. 2011, 40, 4077–4098.
23. Jason A. Halfen, Samiran Mahapatra, Elizabeth C. Wilkinson, Susan Kaderli, Victor G. Young Jr., Lawrence Que, Jr., Andreas D. Zuberbuhler, William B.
Tolman Science 1996, 271, 1397–1400.
24. Lawrence Que, Jr., William B. Tolman Angew. Chem., Int. Ed. 2002, 41, 1114–
1137.
25. Shinobu Itoh, Shunichi Fukuzumi Acc. Chem. Res. 2007, 40, 592–600.
26. Liviu M. Mirica, Michael Vance, Deanne Jackson Rudd, Britt Hedman, Keith O.
Hodgson, Edward I. Solomon, T. Daniel P. Stack Science 2005, 308, 1890–
1892.
27. Copper-Oxygen Chemistry; Karlin, K. D., Itoh, S., Eds.; John Wiley & Sons:
New York, 2011.
28. Alexander Hoffmann, Sonja Herres-Pawlis Chem. Commun. 2014, 50, 403–405.
29. Heather R. Lucas, Lei Li, Amy A. Narducci Sarjeant, Michael A. Vance, Edward I. Solomon, Kenneth D. Karlin J. Am. Chem. Soc. 2009, 131, 3230–3245.
30. Isaac Garcia-Bosch, Anna Company, Jonathan R. Frisch, Miquel Torrent-Sucarrat, Mar Cardellach, Ilaria Gamba, Mireia Gell, Luigi Casella, Lawrence Que, Jr., Xavi Ribas, Josep M. Luis, Miquel Costas Angew. Chem., Int. Ed. 2010, 49, 2406–2409.
31. (a) Kristian E. Dalle, Tim Gruene, Sebastian Dechert, Serhiy Demeshko, Franc Meyer J. Am. Chem. Soc. 2014, 136, 7428–7434. (b) Nicole Kindermann, Eckhard Bill, Sebastian Dechert, Serhiy Demeshko, Edward J. Reijerse, Franc Meyer Angew. Chem., Int. Ed. 2015, 54, 1738–1743.
32. (a) Judith P. Klinman J. Biol. Chem. 2006, 281, 3013–3016. (b) Corinna R. Hess, Judith P. Klinman, Ninian J. Blackburn J. Biol. Inorg. Chem. 2010, 15, 1195–
1207.
33. Sean T. Prigge, Betty A. Eipper, Richard E. Mains, L. Mario Amzel Science 2004, 304, 864–867.
34. Kiyoshi Fujisawa, Masako Tanaka, Yoshihiko Moro-oka, Nobumasa Kitajima J.
Am. Chem. Soc. 1994, 116, 12079–12080.
35. Christian Würtele, Ekaterina Gaoutchenova, Klaus Harms, Max C. Holthausen, Jörg Sundermeyer, Siegfried Schindler Angew. Chem., Int. Ed. 2006, 45, 3867–
3869.
36. (a) Nermeen W. Aboelella, Elizabeth A. Lewis, Anne M. Reynolds, William W.
Brennessel, Christopher J. Cramer, William B. Tolman J. Am. Chem. Soc. 2002, 124, 10660–10661. (b) Anne M. Reynolds, Benjamin F. Gherman, Christopher J.
Cramer, William B. Tolman Inorg. Chem. 2005, 44, 6989–6997.
37. Yuki Kobayashi, Kei Ohkubo, Takashi Nomura, Minoru Kubo, Nobutaka Fujieda, Hideki Sugimoto, Shunichi Fukuzumi, Kei Goto, Takashi Ogura, Shinobu Itoh Eur. J. Inorg. Chem. 2012, 4574–4578.
38. Patrick J. Donoghue, Aalo K. Gupta, David W. Boyce, Christopher J. Cramer, William B. Tolman J. Am. Chem. Soc. 2010, 132, 15869–15871.
39. (a) Peng Chen, David E. Root, Cecelia Campochiaro, Kiyoshi Fujisawa, Edward I. Solomon J. Am. Chem. Soc. 2003, 125, 466–474. (b) Ritimukta Sarangi, Nermeen Aboelella, Kiyoshi Fujisawa, William B. Tolman, Britt Hedman, Keith O. Hodgson, Edward I. Solomon J. Am. Chem. Soc. 2006, 128, 8286–8296. (c) Julia S. Woertink, Li Tian, Debabrata Maiti, Heather R. Lucas, Richard A.
Himes, Kenneth D. Karlin, Frank Neese, Christian Würtele, Max C. Holthausen, Eckhard Bill, Jörg Sundermeyer, Siegfried Schindler, Edward I. Solomon Inorg.
Chem. 2010, 49, 9450–9459. (d) Jake W. Ginsbach, Ryan L. Peterson, Ryan E.
Cowley, Kenneth D. Karlin, Edward I. Solomon Inorg. Chem. 2013, 52, 12872–
12874.
40. Christopher J. Cramer, William B. Tolman Acc. Chem. Res. 2007, 40, 601–608.
41. Ryan L. Peterson, Jake W. Ginsbach, Ryan E. Cowley, Munzarin F. Qayyum, Richard A. Himes, Maxime A. Siegler, Cathy D. Moore, Britt Hedman, Keith O.
Hodgson, Shunichi Fukuzumi, Edward I. Solomon, Kenneth D. Karlin J. Am.
Chem. Soc. 2013, 135, 16454–16467.
42. Claudio Saracini, Dimitrios G. Liakos, Jhon E. Zapata Rivera, Frank Neese,
Gerald J. Meyer, Kenneth D. Karlin J. Am. Chem. Soc. 2014, 136, 1260–1263.
43. Jung Yoon Lee, Ryan L. Peterson, Kei Ohkubo, Isaac Garcia-Bosch, Richard A.
Himes, Julia Woertink, Cathy D. Moore, Edward I. Solomon, Shunichi Fukuzumi, Kenneth D. Karlin J. Am. Chem. Soc. 2014, 136, 9925–9936.
44. Sunghee Kim, Jung Yoon Lee, Ryan E. Cowley, Jake W. Ginsbach, Maxime A.
Siegler, Edward I. Solomon, Kenneth D. Karlin J. Am. Chem. Soc. 2015, 137, 2796–2799.
45. Paolo Pirovano, Adriana M. Magherusan, Ciara McGlynn, Andrew Ure, Amy Lynes, Aidan R. McDonald Angew. Chem., Int. Ed. 2014, 53, 5946–5950.
46. (a) Peng Chen, Edward I. Solomon J. Am. Chem. Soc. 2004, 126, 4992–5000. (b) Peng Chen, Edward I. Solomon Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 13105–
13110.
47. Andrew T. Bauman, Erik T. Yukl, Katsiaryna Alkevich, Ashley L. McCormack, Ninian J. Blackburn J. Biol. Chem. 2006, 281, 4190–4198.
48. Alejandro Crespo, Marcelo A. Martí, Adrian E. Roitberg, L. Mario Amzel, Darío A. Estrin J. Am. Chem. Soc. 2006, 128, 12817–12828.
49. Kazunari Yoshizawa, Naoki Kihara, Takashi Kamachi, Yoshihito Shiota Inorg.
Chem. 2006, 45, 3034–3041.
50. Neil R. McIntyre, Edward W. Lowe, Jr., David J. Merkler J. Am. Chem. Soc.
2009, 131, 10308–10319.
51. Christopher J. Shaffer, Detlef Schröder, Christoph Gütz, Arne Lutzen Angew.
Chem., Int. Ed. 2012, 51, 8097–8100.
52. Ana Conde, Laia Vilella, David Balcells, M. Mar Díaz-Requejo, Agustí Lledós, Pedro J. Pérez J. Am. Chem. Soc. 2013, 135, 3887–3896.
53. Patrick J. Donoghue, Jacqui Tehranchi, Christopher J. Cramer, Ritimukta Sarangi, Edward I. Solomon, William B. Tolman J. Am. Chem. Soc. 2011, 133, 17602–17605.
54. Alison E. Wendlandt, Alison M. Suess, Shannon S. Stahl Angew. Chem., Int. Ed.
2011, 50, 11062–11087.
55. Scott E. Allen, Ryan R. Walvoord, Rosaura Padilla-Salinas, Marisa C.
Kozlowski Chem. Rev. 2013, 113, 6234–6458.
56. (a) Jessica M. Hoover, Shannon S. Stahl J. Am. Chem. Soc. 2011, 133, 16901–
16910. (b) Bradford L. Ryland, Scott D. McCann, Thomas C. Brunold, Shannon S. Stahl J. Am. Chem. Soc. 2014, 136, 12166–12173. (c) Xiaomin Xie, Shannon S. Stahl J. Am. Chem. Soc. 2015, 137, 3767–3770.
57. Jwanro Hassan, Marc Sévignon, Christel Gozzi, Emmanuelle Schulz, Marc Lemaire Chem. Rev. 2002, 102, 1359–1469.
58. Irina P. Beletskaya, Andrei V. Cheprakov Coord. Chem. Rev. 2004, 248, 2337–
2364.
59. Carlo Sambiagio, Stephen P. Marsden, A. John Blacker, Patrick C. McGowan Chem. Soc. Rev. 2014, 43, 3525–3550.
60. Naohiko Yoshikai, Eiichi Nakamura Chem. Rev. 2002, 102, 2339–2372.
61. Robert P. Davies Coord. Chem. Rev. 2011, 255, 1226–1251.
62. Gerard van Koten Organometallics 2012, 31, 7634–7646.
63. T. Cohen, J. Wood, A. G. Dietz, Jr. Tetrahedron Lett. 1974, 15, 3555–3558.
64. (a) D. C. Olson, J. Vasilevskis Inorg. Chem. 1971, 10, 463–470. (b) J. J. Bour, P.
J. M. W. L. Birker, J. J. Steggerda Inorg. Chem. 1971, 10, 1202–1205. (c) Frank P. Bossu, K. L. Chellappa, Dale W. Margerum J. Am. Chem. Soc. 1975, 99,
2195–2203.
65. Alicia Casitas, Xavi Ribas; Insights into the Mechanism of Modern Ullmann–
Goldberg Coupling Reactions. In Copper-Mediated Cross-Coupling Reactions;
Gwilherm Evano, Nicolas Blanchard Eds.; John Wiley & Sons: New Jersey, 2014; pp 263–279.
66. Amanda J. Hickman1, Melanie S. Sanford Nature 2012, 484, 177–185.
67. Alicia Casitas, Xavi Ribas Chem. Sci. 2013, 4, 2301–2318.
68. Kenneth J. Oliver, T. Neil Waters J. Chem. Soc., Chem. Commun. 1982, 1111–
1112.
69. Fred C. Anson, Terrence J. Collins, Thomas G. Richmond, Bernard D.
Santarsiero, James E. Toth, Brian G. R. T. Treco J. Am. Chem. Soc. 1987, 109, 2974–2919.
70. Jan Hanss, Hans-Jörg Krüger Angew. Chem., Int. Ed. Engl. 1996, 35, 2827–
2830.
71. Monika A. Willert-Porada, Donald J. Burton, Norman C. Baenziger J. Chem.
Soc., Chem. Commun. 1989, 1633–1634.
72. Dieter Naumann, Thomas Roy, Karl-Friedrich Tebbe, Wolfgang Crump Angew.
Chem., Int Ed. Engl. 1993, 32, 1482–1483.
73. R. Eujen, B. Hoge, D. J. Brauer J. Organomet. Chem. 1996, 519, 7–20.
74. Igor O. Fritsky, Henryk Kozłowski, Olga M. Kanderal, Matti Haukka, Jolanta Świᶏtek-Kozłowska Elzbieta Gumienna-Konteckab, Franc Meyer Chem.
Commun. 2006, 4125–4127.
75. Stefan Will, Johann Lex, Emanuel Vogel, Hans Schmickler, Jean-Paul Gisselbrecht, Catherine Haubtmann, Maxime Bernard, Maurice Gross Angew.
Chem., Int. Ed. Engl. 1997, 36, 357–361.
76. (a) Hiroyuki Furuta, Hiromitsu Maeda, Atsuhiro Osuka J. Am. Chem. Soc. 2000, 122, 803–807. (b) Hiromitsu Maeda, Yuichi Ishikawa, Tomoyuki Matsuda,
Atsuhiro Osuka, Hiroyuki Furuta J. Am. Chem. Soc. 2003, 125, 11822–11823.
(c) Hiromitsu Maeda, Atsuhiro Osuka, Hiroyuki Furuta J. Am. Chem. Soc. 2003, 125, 15690–15691.
77. (a) Dimitri Coucouvanis; The Chemistry of the Dithioacid and 1,1-Dithiolate Complexes, 1968–1977. In Progress in Inorganic Chemistry, Vol. 26; Stephen J.
Lippard Ed.; John Wiley & Sons: New York, 1979; pp 324–330. (b) Mercouri.
G. Kanatzidis, Norman C. Baenziger, Dimitri Coucouvanis Inorg. Chem. 1985, 24, 2680–2683.
78. José Vicente, Pablo González-Herrero, Yolanda García-Sánchez, Peter G. Jones, Delia Bautista Eur. J. Inorg. Chem. 2006, 115–126.
79. Xavi Ribas, Deanne A. Jackson, Bruno Donnadieu, José Mahía, Teodor Parella, Raül Xifra, Britt Hedman, Keith O. Hodgson, Antoni Llobet, T. Daniel P. Stack Angew. Chem., Int. Ed. 2002, 41, 2991–2994.
80. Lauren M. Huffman, Alicia Casitas, Marc Font, Mercè Canta, Miquel Costas, Xavi Ribas, Shannon S. Stahl Chem.—Eur. J. 2011, 17, 10643–10650.
81. (a) Alicia Casitas, Amanda E. King, Teodor Parella, Miquel Costas, Shannon S.
Stahl, Xavi Ribas Chem. Sci. 2010, 1, 326–330. (b) Amanda E. King, Lauren M.
Huffman, Alicia Casitas, Miquel Costas, Xavi Ribas, Shannon S. Stahl J. Am.
Chem. Soc. 2010, 132, 12068–12073. (c) Xavi Ribas, Carlos Calle, Albert Poater, Alicia Casitas, Laura Gómez, Raül Xifra, Teodor Parella, Jordi Benet-Buchholz, Arthur Schweiger, George Mitrikas, Miquel Solà, Antoni
Llobet, T. Daniel P. Stack J. Am. Chem. Soc. 2010, 132, 12299–12306.
82. (a) Alicia Casitas, Mercè Canta, Miquel Solà, Miquel Costas, Xavi Ribas J. Am.
Chem. Soc. 2011, 133, 19386–19392. (b) Mireia Rovira, Marc Font, Ferran
Acuña-Parés, Teodor Parella, Josep M. Luis, Julio Lloret-Fillol, Xavi Ribas Chem.—Eur. J. 2014, 20, 10005–10010.
83. (a) Bo Yao, De-Xian Wang, Zhi-Tang Huang, Mei-Xiang Wang Chem. Commun.
2009, 2899–2901. (b) Hu Zhang, Liang Zhao, De-Xian Wang, Mei-Xiang Wang Org. Lett. 2013, 15, 3836–3839. (c) Hu Zhang, Bo Yao, Liang Zhao, De-Xian
Wang, Bo-Qing Xu, Mei-Xiang Wang J. Am. Chem. Soc. 2014, 136, 6326–6332.
84. Ruth M. Gschwind Chem. Rev. 2008, 108, 3029–3053.
85. (a) Steven H. Bertz, Stephen Cope, Michael Murphy, Craig A. Ogle, Brad J.
Taylor J. Am. Chem. Soc. 2007, 129, 7208–7209. (b) Steven H. Bertz, Stephen Cope, Donna Dorton, Michael Murphy, Craig A. Ogle Angew. Chem., Int. Ed.
2007, 46, 7082–7085. (c) Erika R. Bartholomew, Steven H. Bertz, Stephen
Cope, Donna C. Dorton, Michael Murphya, Craig A. Ogle Chem. Commun.
2008, 1176–1177. (d) Steven H. Bertz, Michael D. Murphy, Craig A. Ogle,
Andy A. Thomas Chem. Commun. 2010, 46, 1255–1256.
86. Irina P. Beletskaya, Andrei V. Cheprakov Organometallics 2012, 31, 7753–
7808.
87. Robert J. Phipps, Matthew J. Gaunt Science 2009, 323, 1593–1597.
88. Andrew M. Romine, Noel Nebra, Andrey I. Konovalov, Eddy Martin, Jordi Benet-Buchholz, Vladimir V. Grushin Angew. Chem., Int. Ed. 2015, 54, 2745–
2749.
89. Ryoko Santo, Riichi Miyamoto, Rika Tanaka, Takanori Nishioka, Kazunobu
Sato, Kazuo Toyota, Makoto Obata, Shigenobu Yano, Isamu Kinoshita, Akio Ichimura, Takeji Takui Angew. Chem., Int. Ed. 2006, 45, 7611–7614.
90. John D. Franolic, Michelle Millar, Stephen A. Koch Inorg. Chem. 1995, 34, 1981–1982.
91. Jeanet Conradie, Duncan A. Quarless, Jr., Hua-Fen Hsu, Todd C. Harrop, Stephen J. Lippard, Stephen A. Koch, Abhik Ghosh J. Am. Chem. Soc. 2007, 129, 10446–10456.
92. Ya-Ho Chang, Pooi-Mun Chan, Yi-Fang Tsai, Gene-Hsiang Lee, Hua-Fen Hsu Inorg. Chem. 2014, 53, 664–666.
93. (a) Chien-Ming Lee, Chien-Hong Chen, Shyue-Chu Ke, Gene-Hsiang Lee, Wen-Feng Liaw J. Am. Chem. Soc. 2004, 126, 8406–8412. (b) Chien-Hong Chen, Gene-Hsiang Lee, Wen-Feng Liaw Inorg. Chem. 2006, 45, 2307–2316. (c) Chien-Ming Lee, Ya-Lan Chuang, Chao-Yi Chiang, Gene-Hsiang Lee, Wen-Feng Liaw Inorg. Chem. 2006, 45, 10895–10904. (d) Chien-Ming Lee, Tzung-Wen Chiou, Hsin-Hung Chen, Chao-Yi Chiang, Ting-Shen Kuo, Wen-Feng Liaw Inorg. Chem. 2007, 46, 8913–8923. (e) Tzung-Wen Chiou, Wen-Feng Liaw Inorg. Chem. 2008, 47, 7908–7913. (f) Chien-Ming Lee, Chien-Hong Chen, Fu-Xing Liao, Ching-Han Hu, Gene-Hsiang Lee J. Am.
93. (a) Chien-Ming Lee, Chien-Hong Chen, Shyue-Chu Ke, Gene-Hsiang Lee, Wen-Feng Liaw J. Am. Chem. Soc. 2004, 126, 8406–8412. (b) Chien-Hong Chen, Gene-Hsiang Lee, Wen-Feng Liaw Inorg. Chem. 2006, 45, 2307–2316. (c) Chien-Ming Lee, Ya-Lan Chuang, Chao-Yi Chiang, Gene-Hsiang Lee, Wen-Feng Liaw Inorg. Chem. 2006, 45, 10895–10904. (d) Chien-Ming Lee, Tzung-Wen Chiou, Hsin-Hung Chen, Chao-Yi Chiang, Ting-Shen Kuo, Wen-Feng Liaw Inorg. Chem. 2007, 46, 8913–8923. (e) Tzung-Wen Chiou, Wen-Feng Liaw Inorg. Chem. 2008, 47, 7908–7913. (f) Chien-Ming Lee, Chien-Hong Chen, Fu-Xing Liao, Ching-Han Hu, Gene-Hsiang Lee J. Am.