Cationic 2,2′-bipyridine complexes of germanium(ii) and tin(ii)

Abstract

We present the first systematic study of 2,2'-bipyridine complexes of E(ii) cationic acceptors (E = Ge, Sn). The complexes were comprehensively characterized by spectroscopic and crystallographic methods to yield complexes of ECl and E. Computational DFT methods were also employed to survey the bonding in the cations, along with an examination of their molecular orbitals (MOs).

Tris(1‐methyl‐imidazol‐2‐yl)phosphane Complexes of Pnictogen, Tetrel, and Triel Cations

“…One singlet resonance was observed for each mixture in the 31 P NMR spectra, and these are assigned to [P(Im) 3 Sn][OTf] 2 ( δ =−104.9 ppm) and [P(Im) 3 Ge][OTf] 2 ( δ =−125.7 ppm). The 119 Sn NMR spectrum for [P(Im) 3 Sn][OTf] 2 exhibits a singlet at δ =−641.3 ppm, at significantly higher frequency than that of [(bipy) 2 Sn][OTf] 2 ( 119 Sn δ =−728.6 ppm) . The solid‐state structures of [P(Im) 3 Ge][OTf] 2 ⋅ dioxane ⋅ MeCN and [P(Im) 3 Sn][OTf] 2 ⋅ (MeCN) 2 have been determined by X‐ray crystallography.…”

“…This realization has enabled the development of complexes involving p‐block acceptors that are analogous to the vast array of transition‐metal complexes . For example, complexes of Ga + with cryptand, phosphine, pyrazine, or arene ligands, complexes of Ge 2+ with crown ethers, carbenes, ammonia, water, pyridines, phosphines, or isocyanides and complexes of As 3+ with pyridine derivatives demonstrate the diversity of this emerging coordination chemistry. Compounds containing Group 13 metals in the oxidation state +1 (M=Al, Ga, In) are susceptible to disproportionation to form M III and M 0 , as was observed for “GaI” in the presence of bipyridine to yield [Ga(bipy) 3 ][I] 3 and gallium metal .…”

“…This realizationh as enabled the development of complexes involving p-block acceptors that are analogous to the vast array of transition-metal complexes. [1] For example, complexes of Ga + with cryptand, [2] phosphine, [3] pyrazine, [4] or arene [5] ligands, complexes of Ge 2 + with crown ethers, [6] carbenes, [7] ammonia, water, [8] pyridines, [9] phosphines, [10] or isocyanides [11] andc omplexes of As 3 + with pyridine derivatives [12] demonstrate the diversity of this emerging coordination chemistry.C ompounds containing Group13 metals in the oxidation state + 1( M= Al, Ga, In) are susceptible to disproportionation to form M III and M 0 , [13] as was observed for "GaI" [14] in the presence of bipyridine to yield [Ga(bipy) 3 ][I] 3 and gallium metal. [15] Tricationic complexes of indiumh ave only been stabilized with oxygen donors, [16] such as crown ethers [17] and dimethyl sulfoxide, [18] or with 1,3,5-triaminocyclohexane, [19] and the only tricationic complexes of gallium [20] show elaborate EPR spectra.…”

“…The 119 Sn NMR spectrum for [P(Im) 3 Sn] [OTf] 2 exhibits as inglet at d = À641.3 ppm, at significantly higher frequency than that of [(bipy) 2 Sn][OTf] 2 ( 119 Sn d = À728.6 ppm). [9] Thes olid-state structures of [P(Im) 3 Ge] [OTf] 2 ·dioxane·MeCN and [P(Im) 3 Sn][OTf] 2 ·(MeCN) 2 have been determined by X-ray crystallography.…”

Isolation and Reactivity of a Chlorogermyliumylidene Featuring Two Ge–Cl Units

“…Accordingly, chlorogermyliumylidenes [ClGe:] + have been considered as significant key species, as simple substitution of the chlorine atom of [ClGe:] + with suitable nucleophiles (R – ) may readily give rise to various germyliumylidenes [RGe:] + . Indeed, several di‐,, tri‐,, and higher‐coordinate, chlorogermyliumylidene complexes have been developed and structurally characterized over the past decade (Figure ). In terms of the reactivity, it has also been demonstrated that chlorogermyliumylidenes undergo diverse reactions, such as Lewis base adduct formation, oxidation by elemental sulfur,, dechlorinative reduction,, , , Cl/H exchange reaction, as well as salt metathesis reaction,, affording Lewis base adducts, germathioniums, germylones, hydrogermyliumylidene, and phosphaketenylgermyliumylidene or azidogermyliumylidene, respectively.…”