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Abstract
Organodihydridoelement anions of germanium and tin were reacted with metallocene dichlorides of Group 4 metals Ti, Zr and Hf. The germate anion [Ar*GeH2]− reacts with hafnocene dichloride under formation of the substitution product [Cp2Hf(GeH2Ar*)2]. Reaction of the organodihydridostannate with metallocene dichlorides affords the reduction products [Cp2M(SnHAr*)2] (M=Ti, Zr, Hf). ion of a hydride substituent from the titanium bis(hydridoorganostannylene) complex results in formation of cation [Cp2M(SnAr*)(SnHAr*)]+ exhibiting a short Ti–Sn interaction. (Ar*=2,6‐Trip2C6H3, Trip=2,4,6‐triisopropylphenyl).
Highlights
Since Lappert et al invented the synthesis of germylenes and stannylenes in the early 1970s, the interaction of these Lewis basic and Lewis acidic molecules with transition metal fragments has been extensively studied.[1]
The coordination chemistry of low valent tin hydrides was investigated by Rivard et al for the highly reactive SnH2, which was coordinated at transition metals to produce a Lewis base stabilized adduct.[5]
Among a series of metal stannylidyne complexes, Filippou et al reported a synthesis, in which a manganese chlorostannylidene complex was transformed into a stannylidyne complex by abstraction of the chloride substituent from the coordinated chloridoorganostannylene.[28m]. For the synthesis of the Ti-Sn-Ar* moiety we presented here, we employed a closely related approach, by abstracting a hydride substituent from a coordinated hydridoorganostannylene
Summary
Since Lappert et al invented the synthesis of germylenes and stannylenes in the early 1970s, the interaction of these Lewis basic and Lewis acidic molecules with transition metal fragments has been extensively studied.[1]. The hydride chemistry of heavy Group 14 elements and, in particular, the chemistry of low valent elements have recently attracted major interest.[3] Power et al used bulky terphenyl ligands for the synthesis of the first low valent hydrides of tin and germanium.[4] The coordination chemistry of low valent tin hydrides was investigated by Rivard et al for the highly reactive SnH2, which was coordinated at transition metals to produce a Lewis base stabilized adduct.[5] Tilley et al reported the reaction of an osmium benzyl complex with organotin trihydride tripSnH3 (trip = 2,4,6-triisopropylphenyl) to give an organohydridostannylene complex upon toluene elimination.[6] By reacting an NHC adduct of a low valent tin hydride [Ar*SnH(MeNHC)] with the platinum complex [Pt(cod)2] a dimeric tin–platinum complex featuring bridging hydride ligands was characterized at low temperature.[7] We have been exploring the chemistry of organotin and organogermanium trihydrides: Both, reductive elimination of hydrogen in reaction with various Lewis bases, as well as hydride abstraction to give highly reactive dihydridocations were studied.[8] deprotonation with Brønsted bases, such as LiMe, LDA or KBn was investigated, which resulted in the formation of organodihydrido anions of germanium and tin.[9]. The homologous tin anion 3 was reacted with metallocene dichlorides of titanium, zirconium and hafnium (Scheme 2) to give the titanium bis(stannylene) complex 4 in high yield (96 %), whereas the zirconium and hafnium analogues were isolated in moderate yield (5: 69 %; 6: 42 %)
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