The Ruthenostannylene Complex [Cp*(IXy)H₂Ru‐Sn‐Trip]: Providing Access to Unusual Ru‐Sn Bonded Stanna‐imine, Stannene, and Ketenylstannyl Complexes

Abstract

Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2 Ru-Sn-Trip] (1; IXy=1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; Cp*=η(5) -C5 Me5 ; Trip=2,4,6-iPr3 C6 H2 ) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β-unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2 RuSn(κ(2) -O,O-OCPhCPhO)Trip] (2) and [Cp*(IXy)(H)2 RuSn(κ(2) -O,C-OCPhCHCHPh)Trip] (3), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin-substituted ketene complex [Cp*(IXy)(H)2 RuSn(OC2 H5 )(CHCO)Trip] (4), which is most likely a decomposition product from the putative ruthenium-substituted stannene complex. The isolation of a ruthenium-substituted stannene [Cp*(IXy)(H)2 RuSn(=Flu)Trip] (5) and stanna-imine [Cp*(IXy)(H)2 RuSn(κ(2) -N,O-NSO2 C6 H4 Me)Trip] (6) complexes was achieved by treatment of 1 with 9-diazofluorene and tosyl azide, respectively.

Donor-Promoted 1,2-Hydrogen Migration from Silicon to a Saturated Ruthenium Center and Access to Silaoxiranyl and Silaiminyl Complexes

“…Complexes 7 and 10 both exhibit two hydride resonances (−10.26 and −10.53 ppm for 7 ; −10.61 and −10.89 ppm for 10 ) with no observable silicon satellites in the 1 H NMR spectra (benzene- d 6 ) and 29 Si resonances at 26.7 (for 7 ) and 68.9 (for 10 ) ppm. For comparison, the ruthenostannylene ( 2 ) exhibits analogous reactivity toward E -1,3-diphenyl-2-propen-1-one and forms the cycloaddition product Cp*­(IXy)­(H) 2 RuSn­(κ 2 - O ,C- O CPhCH C HPh)­Trip . Taken together, this reactivity suggests that metallosilylenes 3b and 4b (Scheme ) might be intermediates in the formation of cycloaddition products 7 and 10 . …”

“…Note that the recently reported ruthenostannaimine Cp*­(IXy)­(H) 2 RuSn­(κ 2 - N , O -NSO 2 C 6 H 4 Me)­Trip features coordination of the oxygen atom of the Ts group to stabilize the electron deficient SnN moiety. This is probably due to less effective Ru–H bond donation to the tin center owing to a longer Ru–Sn distance …”

Heavy Tetrel Complexes of Ru Featuring Ru═E(R)X and Ru–E–R (E = Sn, Pb) Linkages

“…Silylene complexes have long been proposed as catalytic intermediates in important reactions such as silane redistribution − and hydrosilation. − A detailed understanding of the structures and reactivities of silylene complexes has been enhanced by investigations of the heavier congeners involving Ge, Sn, and Pb, which provide insights into multiple-bonding interactions between metals and group 14 elements and point to new reactivity patterns for unsaturated metal–main-group complexes. − …”

Dimeric platinum–stannylene complexes by twofold ligand transfer from an NHC adduct to an organotin(ii) hydride

“…Regarding Sn(II), numerous examples of stannylene complexes [(R 2 Sn) n ML] (R = non-p-basic alkyl, aryl, silyl; n = 1, 2, 4, M = various transition metals) revealed the s-donating/p-accepting character of the stannylene. 3c,e, 5 We recently presented a protocol for straightforward synthesis of NHC adducts to stannylenes R 2 Sn (R = Ph, trip) and hydrostannylenes (RSnH, R = Ar*, trip) by stoichiometric abstraction of dihydrogen. 2 Further Sn-M interaction modes can be realized in metallostannylenes [L 0 Sn-ML n ] (L 0 = monodentate Ar, M = Cr, Mo, W, Mn, Fe, Ru, Os) 3 and were also subject of computational investigations.…”