Preparation and Reactivity of Stannyl Complexes of Ruthenium(II) Stabilized by an Indenyl Ligand

Abstract

Trichlorostannyl 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+CCPh– in THF yielded the trialkynylstannyl compounds Ru[Sn(CCPh)3](η5-C9H7)(PPh3)L (4). Treatment of the trihydridostannyl complexes 2 with the alkyl propiolate HCCCOOR 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 HCCCPh2OH yielded the alkene H2CC(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(CCPh)3](η5-C9H7)(PPh3)[P(OEt)3] (4b) and Ru[Sn(OH)3](η5-C9H7)(PPh3)[P(OEt)3] (8b).

Nucleophilic Additions to Allenylidene Ruthenium Complexes

“…These complexes have been recently synthesized in 75% yield when the same reaction is carried out in refluxing THF. Analytical and spectroscopic data agree with those reported in the literature …”

Preparation and reactivity of diazoalkane complexes of ruthenium stabilised by an indenyl ligand

“…Indenyl complexes [RuCl(η 5 -C 9 H 7 )(PPh 3 ) 2 ] and [RuCl(η 5 -C 9 H 7 )-(PPh 3 ){P(OR) 3 }] (R = Me, Et) were prepared following the method previously reported. 36,37 [Ru(η 5 -C 9 H 7 )(N 2 CAr1Ar2)(PPh 3 ) 2 ]BPh 4 (1) [Ar1 = Ph, Ar2 = p-tolyl (b); Ar1Ar2 = C 12 H 8 (c)]. In a 25 mL three-necked round-bottomed flask were placed solid samples of [RuCl-(η 5 -C 9 H 7 )(PPh 3 ) 2 ] (0.10 g, 0.13 mmol), an excess of the appropriate diazoalkane N 2 CAr1Ar2 (0.40 mmol), an excess of NaBPh 4 (0.26 mmol, 89 mg), 7 mL of ethanol and 5 mL of dichloromethane.…”

Stannyl Complexes of Rhodium and Iridium: Preparation of Mono‐ and Bis(trihydridestannyl) Derivatives

“…The use of NaBH 4 as a reagent to prepare tin trihydride complexes turns out to be an interesting synthetic method in tin chemistry that we had previously used to synthesise several [M]–SnH 3 derivatives ,,,,,,. In the present study, this route allowed the preparation of the first iridium complexes containing tin trihydride as a ligand.…”

“…In the present study, this route allowed the preparation of the first iridium complexes containing tin trihydride as a ligand. As observed with other stannyl derivatives,,,, the nature of the central metal and the ancillary ligands seem to be crucial for stabilising tin trihydride complexes. The pentamethylcyclopentadienyl half‐sandwich fragment with phosphite ligand is able to stabilise both mono‐ and bis(tin trihydride) derivatives, but only with iridium.…”