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- Title
Homo- and Heterodinuclear Rh and Ir Complexes Supported by SN <sub>n</sub> Mixed-Donor Ligands ( n = 2-4): Stereochemistry and Coordination-Site-Exchange Reactions of Cp*M (M = Rh, Ir) Units.
- Authors
Nakajima, Takayuki; Kawasaki, Yuki; Kure, Bunsho; Tanase, Tomoaki
- Abstract
A series of SN n mixed-donor ligands [ n = 2: H2NC2H4SCH2-2-pyridyl (2-NSpy) ( 1a), H2NC2H4SCH2-4-pyridyl (4-NSpy) ( 1b), n = 3: 2-pyridylCH2NHC2H4SCH2-2-pyridyl (2-pyNSpy) ( 2), n = 4: (2-pyridylCH2)2NC2H4SCH2-2-pyridyl (2-py2NSpy) ( 3)] was utilized to support homo- and heterodinuclear complexes including Cp*MIII units (M = Rh, Ir; Cp* = pentamethylcyclopentadienyl). Reactions of [Cp*MCl2]2 with 2-pyNSpy ( 2), 2-py2NSpy ( 3), and 4-NSpy ( 1b) afforded homodinulear complexes, [(Cp*MCl)(2-pyNSpy)(Cp*MCl)](PF6)2 [M = Rh ( 5a), Ir ( 5b)], [(Cp*M)(2-py2NSpy)(Cp*MCl)](PF6)3 [M = Rh ( 6a), Ir ( 6b)], [(Cp*MCl)(4-NSpy)(Cp*MCl2)]Cl [M = Rh ( 8a), Ir ( 8b)]. Heterodinuclear complexes [(Cp*MCl)(4-NSpy)(Cp*M′Cl2)]Cl [M, M′ = Rh, Ir ( 8c), Ir, Rh ( 8d)] were prepared using mononuclear complexes [(Cp*MCl)(4-NSpy)]Cl [M = Rh ( 7a), Ir ( 7b)] reacted with [Cp*MCl2]2 (M = Ir, Rh), respectively. Complexes 5- 8 were characterized by X-ray crystallography to determine the configurations around the M, M′, S, and N centers. The solid-state structures of 6 are retained in acetonitrile solution whereas four diastereomers are generated in the case of 5 due to low stereoselectivity around the coordinated amine nitrogen atom, in contrast to the sulfur atom. Heterodinuclear complexes 8c, d are unstable in solution at 55 °C, readily affording mixtures of 8a- d via intra- and intermolecular coordination-site-exchange reactions of Cp*M fragments between the SN moiety and the py site. In order to evaluate the selectivity of Cp*M fragments for the SN and py coordination sites, several competitive reactions of [Cp*MCl2]2 (M = Rh, Ir) with H2NC2H4SCH2C6H5 (NSph) ( 4) and/or 4-methylpyridine (4-Mepy) were carried out to demonstrate predominant formation of iridium complexes 9b and 10b among [(Cp*MCl)(NSph)]Cl [M = Rh ( 9a), Ir ( 9b)] and [(Cp*MCl)(4-Mepy)]Cl [M = Rh ( 10a), Ir ( 10b)]. These reactions indicated higher affinity of the Cp*Ir fragment to both the NS and py sites relative to the rhodium analogue.
- Subjects
LIGANDS (Chemistry); COORDINATION compounds; DIASTEREOISOMERS; SULFUR; NATIVE element minerals
- Publication
European Journal of Inorganic Chemistry, 2016, Vol 2016, Issue 28, p4701
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201600722