A stable and long-lived germaimine

Reactions of bis[bis(trimethylsilyl)methyl]germylene and the corresponding stannylene with diazidosilanes

“…Compound 4 is stable in solution in the absence of air. In the 'H NMR spectrum, the appearance of only one signal for the trimethylsilyl groups is similar to the observations with other stable germanimines [7]. The low field shifted 13C resonance at 6 = 32 (in C6D6) of the methine carbon atom, as well as the high field shifted 29Si res- onance of the 'Bu,Si unit at S = -10, indicates a strong polarity of the germanimine moiety (Ge'-N-).…”

Germanium-carbon versus germanium-nitrogen double-bond formation in the reactions between germylenes and diazo compounds

“…On the basis of the results described in this contribution, we predict that, whereas the reactions of diazo compounds with [(Me3Si)zN]zGe are dominated by products containing Ge=N bonds [1][2][3][4], these with the closely similar [(Me3Si)zCH]2Ge will be dominated by products containing Ge~C bonds.…”

“…The electron-rich germylene [(Me3Si)2N]2Ge reacts with a wide range of diazo compounds N2C(R1)R2 to form initially 1:1 adducts containing Ge=N bonds [1][2][3][4]: these bonds are polarized in the sense Ge~+-N 8-, and the adducts are easily trapped by means of addition reactions with weak acids HX to form readily isolable products [(Me3Si)zN]zGe(X)NHNC(R1)R2. Prior to reaction with HX, the adducts can in a number of cases [2,3,5] be characterized in solution by IH and 13C NMR spectroscopy: when R1 = R2 = COOMe, two isomeric forms of the adduct were observed [2,3] and identified [4] as, respectively, the planar acyclic transoid form (1) and the cyclic cisoid form (2) (see Scheme 1).…”

“…Prior to reaction with HX, the adducts can in a number of cases [2,3,5] be characterized in solution by IH and 13C NMR spectroscopy: when R1 = R2 = COOMe, two isomeric forms of the adduct were observed [2,3] and identified [4] as, respectively, the planar acyclic transoid form (1) and the cyclic cisoid form (2) (see Scheme 1). Subsequent 1,2-addition of HX to the isomer (2) provides (3), characterized by X-ray crystallography [3] for the case of HX = HC(Nz)COPh. With the diazo compound NzC(COCH3)COOEt, the analogous electron-rich stannylene [(Me3Si)zN]2Sn likewise forms a product [6] that results from initial formation of an adduct containing an Sn=N bond, followed by an intramolecular 1,2-addition across this bond.…”

“…Following our MNDO study [4] of the isomeric forms of [(Me3Si)zN]2GeNNC(COX)(COY) (X, Y = Me, OMe) and of subsequent inter-and intramolecular addition reactions to the unique germanium-nitrogen bond, which established a plausible sequence of iv~ter-mediates between the reactants and the observed products [1][2][3], we have now investigated computationally the possibility of both germanium-nitrogen and germanium-carbon bond formation in the reactions of…”