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Alkynethiolato and Alkyneselenolato Ruthenium Half-Sandwich Complexes: Synthesis, Structures, and Reactions with (η5-C5H5)2Zr

Authors :
Yuji Hayashi
Yusuke Sunada
Hiroyuki Kawaguchi
Kazuyuki Tatsumi
Source :
Inorganic Chemistry. 40:7072-7078
Publication Year :
2001
Publisher :
American Chemical Society (ACS), 2001.

Abstract

Alkynethiolato and alkyneselenolato complexes of ruthenium, CpRu(PPh(3))(2)(EC(triple bond)CR) (Cp = eta(5)-C(5)H(5); E = S, R = Ph (1a), SiMe(3) (1b), (t)Bu (1c); E = Se, R = Ph (2a), SiMe(3) (2b)), were synthesized by the reactions of CpRuCl(PPh(3))(2) with corresponding lithium alkynechalcogenolates in THF. An analogous reaction of Cp*RuCl(PEt(3))(2) (Cp* = eta(5)-C(5)Me(5)) with LiSC(triple bond)CPh produced Cp*Ru(PEt(3))(2)(SC(triple bond)CPh) (3). Complexes 1a and 2a were allowed to react in THF with "Cp(2)Zr", generated in situ from Cp(2)ZrCl(2) and 2 equiv of n-BuLi, from which the S-bridged Ru-Zr dinuclear complexes CpRu(PPh(3))(C(triple bond)CPh)(mu-S)ZrCp(2) (4a) and CpRu(PPh(3))(C(triple bond)CPh)(mu-Se)ZrCp(2) (4b) were isolated, respectively. In these complexes, C-S(Se) bond cleavage of the alkynechalcogenolate ligands was promoted by "Cp(2)Zr", and the Zr atom was oxidized from II to IV. Treatment of 4a and 4b in THF under 1 atm CO gave rise to CpRu(CO)(C(triple bond)CPh)(mu-E)ZrCp(2) (E = S (5a), Se (5b)), while addition of tert-butyl isocyanide to a THF solution of 4b afforded CpRu(CN(t)()Bu)(C(triple bond)CPh)(mu-Se)ZrCp(2) (6). The crystal structures of 1a, 1c, 2a, 2b, 3, 4a, 4b, and 5b were determined by X-ray diffraction analysis.

Details

ISSN :
1520510X and 00201669
Volume :
40
Database :
OpenAIRE
Journal :
Inorganic Chemistry
Accession number :
edsair.doi.dedup.....b7dfaddbe2627c47abbf2a64cb1a9fe2
Full Text :
https://doi.org/10.1021/ic010826h