Reaction of 3‐dimethylamino‐(1,1 ‐dimethyl) propyl magnesium chloride with tin (IV) and tin (II) chlorides. Stabilization of a SnCl⁺ cation in the new tin cluster [Me₂NCH₂CH₂C(Me₂)SnCl]₃ · SnCl₂

Abstract

The reactions of the functional Grignard reagent Me2 NCH2CH2C(Me2)MgCl (4) with tin tetrachloride, dimethyltin dichloride, and tin (II) chloride are described. From the reactions the compounds bis(3‐dimethylamino‐1,1‐dimethylpropyl) tin dichloride, [Me2NCH2CH2C(Me2)]2SnCl2 (5), dimethyl(3‐dimethylamino‐1,1‐dimethylpropyl) chlorostannane, Me2ClSnC(Me2)CH2CH2NMe2 (6), 1,1,2,2‐tetramethyl‐1,2‐bis(3‐dimethylamino‐1,1‐dimethylpropyl) distannane,[Me2SnC(Me2)CH2CH2NMe2]2 (7), 3‐dimethylamino‐(1,1‐dimethyl)propyl tin (II) chloride, Me2NCH2CH2C(Me2)SnCl (8), hexakis(3‐dimethylamino‐1,1‐dimethylpropyl) cyclotristannane, {[Me2NCH2CH2C(Me2)]2Sn}3(9a), and the tin cluster [Me2NCH2CH2C(Me2)SnCl]3 · SnCl2 (10) have been isolated and characterized by means of multinuclear NMR and Mössbauer spectroscopy, and X‐ray diffraction. 10 crystallizes in the trigonal space group P31 with the unit cell dimensions a 11.938, c 21.873 Å, V 2699.6 Å3 Z = 3. The structure was refined to a final R value of 0.064. 10 represents a tetranuclear cluster the skeleton of which is composed out of 4 Sn and a bridging Cl. Formally, the central tin atom is a SnCl+ cation stabilized by three stannylene units in a Ψ‐trigonal bipyramidal environment. The tin‐tin bond lengths are 288.2, 287.3 and 315.6 pm. The intramolecular SnN interactions amount to 242.8, 247.4 and 221.0 pm.

Reduction of C,N-chelated Diorganotin(IV) Dichlorides

“…4. There is no contact between tin atoms Sn1, Sn2, and Sn3, which enables us to compare 10 with previously published compounds cyclo-[(L CN 2 Sn) 2 -m-(SnL CN )-m-(OH)] [15], [Me 2 NCH 2 CH 2 C(Me) 2 SnCl] 3 .SnCl 2 [16] and a triply chelated Sn(IV)e Sn(II)eCl [17] complex which are the only proposed complexes of such type. The Sn4 atom is located 1.596 Å above the plane determined by Sn1, Sn2, and Sn3 atoms.…”

Monoanionic Tin Oligomers Featuring Sn–Sn or Sn–Pb Bonds: Synthesis and Characterization of a Tris(Triheteroarylstannyl)Stannate and -Plumbate

“…Thus, in 3, the central lead atom is significantly more shielded according to a smaller contribution to the paramagnetic contribution term. In addition, fast fluctuation of the lithium counterion in 2 or 3 can be attributed to a upfield shifting of the 7 Li NMR resonances to +0.68 ppm (2) and +1.08 ppm (3) in comparison to the parent lithium stannate 1 (δ = +2.12 ppm).…”

“…Hence, homonuclear as well as heteronuclear molecules with E-E bonds become less stable when E represents tin and or lead. Moreover, within this class of compounds, discrete branched oligomers with more than one E-E bond are rare compared with their linear analogs [6][7][8][9][10]. It has been shown that reactions of lead(II) halides with Grignard reagents involved disproportionation processes leading to plumbates of type [MgBr(THF) 5 3 ] (Bp = 4-Biphenyl) [12].…”

CisversusTrans: The Coordination Environment about the Tin(IV) Atom in Spirocyclic Amino Alcohol Derivatives

“…Especially the coordination mode about the tin atom and the strength of the intramolecular N→Sn coordination as a function of the identity of the substituents R and R′ were studied . With growing environmental awareness, nontoxic inorganic tin compounds lacking any tin–carbon bonds are in the focus of research . Amino alcoholate derivatives of tin are such inorganic compounds.…”