om400273y_si_001.cif (53.9 kB)
Preparation and Reactivity of Stannyl Complexes of Ruthenium(II) Stabilized by an Indenyl Ligand
dataset
posted on 2013-07-08, 00:00 authored by Gabriele Albertin, Stefano Antoniutti, Jesús Castro, Sebastiano Da LioTrichlorostannyl complexes Ru(SnCl3)(η5-C9H7)(PPh3)L (1; L
= P(OMe)3, P(OEt)3) were prepared by allowing
chloro compounds RuCl(η5-C9H7)(PPh3)L to react with SnCl2·2H2O in ethanol. Treatment of compounds 1 with NaBH4 in ethanol yielded the tin trihydride derivatives Ru(SnH3)(η5-C9H7)(PPh3)L (2). The reaction of trichlorostannyl complexes 1 with MgBrMe in diethyl ether afforded the chlorodimethylstannyl
derivatives Ru(SnClMe2)(η5-C9H7)(PPh3)L (3), whereas reaction
with Li+CCPh– in THF yielded
the trialkynylstannyl compounds Ru[Sn(CCPh)3](η5-C9H7)(PPh3)L (4). Treatment of the trihydridostannyl complexes 2 with
the alkyl propiolate HCCCOOR led to the trivinylstannyl derivatives
Ru[Sn{C(COOR)CH2}3](η5-C9H7)(PPh3)L (5, 6; R = Me, Et). However, the reaction of [Ru]–SnH3 (2) with the propargylic alcohol HCCCPh2OH yielded the alkene H2CC(H)CPh2OH and the hydride RuH(η5-C9H7)(PPh3)L (7). Treatment of tin trihydride
complexes 2 with H2O led to the trihydroxostannyl
derivatives Ru[Sn(OH)3](η5-C9H7)(PPh3)L (8). Protonation of
[Ru]–SnH3 (2) with triflic acid (HOTf)
produced the very unstable dihydridostannyl compound Ru[SnH2(OTf)](η5-C9H7)(PPh3)L (9). Stabilization of SnH2 species was
achieved by protonation with HOTf at −30 °C of the cyclopentadienyl
compound Ru(SnH3)(η5-C5H5)(PPh3)[P(OMe)3], which yielded the
complex Ru[SnH2(OTf)](η5-C5H5)(PPh3)[P(OMe)3] (10a). The complexes were characterized by spectroscopy (IR and 1H, 31P, 13C, and 119Sn NMR
data) and by X-ray crystal structure determinations of Ru[Sn(CCPh)3](η5-C9H7)(PPh3)[P(OEt)3] (4b) and Ru[Sn(OH)3](η5-C9H7)(PPh3)[P(OEt)3] (8b).