Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/17117
Title: Synthesis, structure, and reactivity of trigonal bipyramidal ruthenium(IV) trialkyl complexes
Authors: Kwan Huang, E
Cheung, WM
Chan, SLF 
Sung, HHY
Williams, ID
Leung, WH
Issue Date: 2013
Publisher: American Chemical Society
Source: Organometallics, 2013, v. 32, no. 16, p. 4483-4489 How to cite?
Journal: Organometallics 
Abstract: The alkylation of [Ru(NPPh3)(PPh3)2Cl 3] with Me3SiCH2MgCl afforded the Ru IV trialkyl complex [Ru(CH2SiMe3) 3(PPh3)Cl] (1), which exhibits a trigonal bipyramidal geometry with the three alkyl groups occupying the equatorial plane. DFT calculations reveal that 1 possesses a (dxz,dyz)4 singlet ground state, consistent with the observed diamagnetism of the complex. The electronic spectrum of 1 displayed two absorptions at 455 and 505 nm, which, on the basis of TDDFT calculations, are attributed to metal-centered d-d transitions with a significant contribution from the alkyl ligands. Chloride abstraction of 1 with Ag(OTf) (OTf- = triflate) provided the triflate complex [Ru(CH2SiMe3)3(PPh3)(OTf)] (2) that proved to be a useful starting material for RuIV trialkyl complexes. Substitution of 2 with NaX afforded [Ru(CH2SiMe 3)3(PPh3)(X)] (X = N3 - (3) or SCN- (4)). Treatment of 2 with excess sodium 2,3,5,6-tetrafluorophenoxide (NaORf) in tetrahydrofuran resulted in desilylation of two alkyl groups, and formation of the dimethyl complex [Ru(CH2SiMe3)Me2(PPh3)(OR f)] (5). 2 underwent reductive elimination of the C-C bond with 1,10-phenanthroline (phen) in CH2Cl2 to give cis-[Ru(phen)2(PPh3)Cl](OTf) (6). The crystal structures of 1, 2, 4, and 5 have been determined.
URI: http://hdl.handle.net/10397/17117
ISSN: 0276-7333
EISSN: 1520-6041
DOI: 10.1021/om400183n
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