Investigation of New Coordination Modes for Coordinatively Unsaturated (Dithiolato)cobalt(III) Complex [(5-Cp)Co(1,2
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- 作者：Jae-Hong Won ; Dae-Hyun Kim ; Bo Young Kim ; Sung-Joon Kim ; Chongmok Lee ; Sungil Cho ; Jaejung Ko ; and Sang Ook Kang
- 刊名：Organometallics
- 出版年：2002
- 出版时间：April 1, 2002
- 年：2002
- 卷：21
- 期：7
- 页码：1443 - 1453
- 全文大小：173K
- 年卷期：v.21,no.7(April 1, 2002)
- ISSN：1520-6041
文摘
A mononuclear 16-electron Cp-cobalt(III)-dithiolate complex of the general formula [(
5-Cp)Co(CabS,S')] (2) (CabS,S' = 1,2-S2C2B10H10-S,S') has been prepared by treatment of CpCo(CO)I2 with the corresponding dilithium dithiolato ligand Li2CabS,S' (1). Experiments aimedat the characterization of new coordination modes for 2 are described. The reaction of 2with BH3·THF produces an unexpected bimetallic cobalt dithiolate complex, [((5-Cp)Co)2(CabS,S')] (3). A second new bonding mode for 2 was generated by treatment of 2 with Lewisbases (L) to give [(5-Cp)Co(CabS,S')(L)] (L = CNBut (4a), PEt3 (4b)), the 18-electron speciesof which consists of a mononuclear 2 coordinated through a dative Co-L bond. A third newbonding mode for 2 is illustrated by [(5-Cp)Co(CabS,S')(1-CH2SiMe3-S)] (5). Reaction of 2with (trimethylsilyl)diazomethane resulted in the formation of the alkylidene-bridged complex5, containing a Co-C-S three-membered ring. The formation of 4 and 5 has also beeninvestigated electrochemically. Consequently, the addition of organic and organometalliccompounds into the Co-S bond of 2 has been investigated. Thus, the syntheses of half-sandwich cobalt(III) complexes [(5-Cp)Co(CabS,S')(L)] [L = 5-CpCo-S,S' (3), 1-R1C=CR2-S(6: R1 = R2 = COOMe (6a); R1 = H R2 = Ph (6b); R1 = H R2 = SiMe3 (6c))] are reported. Inaddition, the solid-state structures of 3, 4b, 5, and 6a were characterized by single-crystalX-ray analyses.
5-Cp)Co(CabS,S')] (2) (CabS,S' = 1,2-S2C2B10H10-S,S') has been prepared by treatment of CpCo(CO)I2 with the corresponding dilithium dithiolato ligand Li2CabS,S' (1). Experiments aimedat the characterization of new coordination modes for 2 are described. The reaction of 2with BH3·THF produces an unexpected bimetallic cobalt dithiolate complex, [((5-Cp)Co)2(CabS,S')] (3). A second new bonding mode for 2 was generated by treatment of 2 with Lewisbases (L) to give [(5-Cp)Co(CabS,S')(L)] (L = CNBut (4a), PEt3 (4b)), the 18-electron speciesof which consists of a mononuclear 2 coordinated through a dative Co-L bond. A third newbonding mode for 2 is illustrated by [(5-Cp)Co(CabS,S')(1-CH2SiMe3-S)] (5). Reaction of 2with (trimethylsilyl)diazomethane resulted in the formation of the alkylidene-bridged complex5, containing a Co-C-S three-membered ring. The formation of 4 and 5 has also beeninvestigated electrochemically. Consequently, the addition of organic and organometalliccompounds into the Co-S bond of 2 has been investigated. Thus, the syntheses of half-sandwich cobalt(III) complexes [(5-Cp)Co(CabS,S')(L)] [L = 5-CpCo-S,S' (3), 1-R1C=CR2-S(6: R1 = R2 = COOMe (6a); R1 = H R2 = Ph (6b); R1 = H R2 = SiMe3 (6c))] are reported. Inaddition, the solid-state structures of 3, 4b, 5, and 6a were characterized by single-crystalX-ray analyses.