Dinuclear Pyridine-4-thiolate-Bridged Rhodium and Iridium Complexes as Ditopic Building Blocks in Molecular Architecture
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- 作者：Montserrat Ferrer ; Daniel Gómez-Bautista ; Albert Gutiérrez ; José R. Miranda ; Guillermo Ordu?a-Marco ; Luis A. Oro ; Jesús J. Pérez-Torrente ; Oriol Rossell ; Pilar García-Ordu?a ; Fernando J. Lahoz
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：February 3, 2014
- 年：2014
- 卷：53
- 期：3
- 页码：1699-1711
- 全文大小：668K
- ISSN：1520-510X
文摘
A series of dinuclear pyridine-4-thiolate (4-Spy)-bridged rhodium and iridium compounds [M(渭-4-Spy)(diolef)]2 [diolef = 1,5-cyclooctadiene (cod), M = Rh (1), Ir (2); diolef = 2,5-norbornadiene (nbd), M = Rh (3)] were prepared by the reaction of Li(4-Spy) with the appropriate compound [M(渭-Cl)(diolef)]2 (M = Rh, Ir). The dinuclear compound [Rh(渭-4-Spy)(CO)(PPh3)]2 (4) was obtained by the reaction of [Rh(acac)(CO)(PPh3)] (acac = acetylacetonate) with 4-pySH. Compounds 1鈥?b>4 were assessed as metalloligands in self-assembly reactions with the cis-blocked acceptors [M(cod)(NCCH3)2](BF4) [M = Rh (a), Ir (b)] and [M(H2O)2(dppp)](OTf)2 [M = Pd (c), Pt (d); dppp = 1,3-bis(diphenylphosphino)propane]. The homometallic hexanuclear metallomacrocycles [{M2(渭-4-Spy)2(cod)2}2{M(cod)}2](BF4)2 (M = Rh [(1a)2], Ir [(2b)2]) and the heterometallic hexanuclear metallomacrocycles [{Rh2(渭-4-Spy)2(cod)2}2{Ir(cod)}2](BF4)2 [(1b)2], [{Rh2(渭-4-Spy)2(cod)2}2{M鈥?dppp)}2](OTf)4 (M鈥?= Pd [(1c)2], Pt [(1d)2]), and [{Ir2(渭-4-Spy)2(cod)2}2{M鈥?dppp)}2](OTf)4 (M鈥?= Pd [(2c)2], Pt [(2d)2]) were obtained. NMR spectroscopy in combination with electrospray ionization mass spectrometry was used to elucidate the nature of the metalloligands and their respective supramolecular assemblies. Most of the synthesized species were found to be nonrigid in solution, and their fluxional behavior was studied by variable-temperature 1H NMR spectroscopy. An X-ray diffraction study of the assemblies (1a)2 and (1d)2 revealed the formation of rectangular (9.6 脜 脳 6.6 脜) hexanuclear metallomacrocycles with alternating dinuclear (Rh2) and mononuclear (Rh or Pt) corners. The hexanuclear core is supported by four pyridine-4-thiolate linkers, which are bonded through the thiolate moieties to the dinuclear rhodium units, exhibiting a bent-anti arrangement, and through the peripheral pyridinic nitrogen atoms to the mononuclear corners.