Di(fluorosulfato)‐di(acetonitril)dimethylzinn(IV) [Me₂Sn(OSO₂F)₂(NCMe)₂]: Bildung und molekülstruktur

Abstract

Inhaltsiibersicht. Ein Einkristall des Titelkomplexes (4) ent-phischer Inversionssymmetrie (Sn-C 209,2, Sn-0 225,8, stand zufallig bei Versuchen, rontgentaugliche Kristalle der Sn-N 235,9 pm, &-Winkel 87-93'). Die als einzahniger bekannten Verbindung Me2Sn[N(S02F)2]2 (3) aus Acetoni-0-Ligand wirkende FS03-Gruppe weicht nicht stark von C3vtril zu zuchten. Die thermolabile Substanz 4 kann gezielt aus Symmetrie ab (Mittelwerte: S-0 143,4, S-F 156,8pm, 0-S-0 114,9, Me2Sn(OS02F)2 und MeCN dargestellt werden. Die Kri-F-S-0 103,3"). Als neues Darstellungsverfahren fur 3 wird stallpackung von 4 (monoklin, Raumgruppe P21/n) besteht die Metathese von Me2SnC12 rnit AgN(S02F), . C6H6 beschrieaus all-trans-oktaedrischen Formeleinheiten rnit kristallogra-ben. Di(fluorosu1fato)-di( ace tonitri1e)dime thyltin(1V) [ Me2Sn( 0 S02F)2( NCMe)2]: Formation and Molecular Structure Abstract. A single crystal of the title complex (4) was formed accidentally in an attempt to grow crystals of the known compound Me2Sn[N(S02F)2]2 (3) from acetonitrile. Bulk quantities of the thermally labile species 4 can be obtained from scribed. Me2Sn(OS02F)2 and MeCN. The structure of 4 (monoclinic, space group P21/n) consists of all-trans octahedral formula units displaying crystallographic centrosymmetry (Sn-C 209.2, Keywords: Difluorosu1fato)-di( acetonitrile)dimethyltin(IV); Sn-0 225.8, Sn-N 235.9 pm, cis-angles 87-93'). The 0-monodimethyltin(1V)-his[di(fluorosul€onyl)amide]; synthesis; Xdentate FS03 ligand does not deviate significantly from ray structure C3v symmetry (mean dimensions: S-0 143.4, S-F 156.8 pm, 0-S-0 114.9, F-S-0 103.3"). For 3, a new synthesis involving metathesis of MezSnClz with AgN(S02F), . C6H6 is de-

Reactions of Dimethyl Sulfite with Diorganotin Oxides. One-Pot Synthesis of Methoxydiorganotin Methanesulfonates through the Arbuzov Rearrangement, Spectroscopic Characterization of These Compounds and Their Derivatives, and X-ray Crystal Structures of n-Bu2Sn(X)OS(O)2Me (X = acac, bzbz, OH)

“…The planar angles of the SnO 4 core group sum to 360 ± 0.1° in these compounds. The O−S−O angles of the methanesulfonate groups are similar to those found in other related organotin derivatives. − …”

“…However, these are comparable to the corresponding Sn−O bond distances reported for hydroxodi- n -butyltin perchlorate [2.425(5) Å] 11 and hydroxodimethyltin nitrate [2.30(3) Å], reflecting appreciable ionic character for these bonds. Sn−C and S−O bond distances are normal. − The presence of the S−C bond [1.721(7) Å for 6 ; 1.744(13), 1.742(11) Å for 10 ] conclusively proves the identity of methanesulfonate group in these compounds. The Sn···Sn bond distances (4.816−4.986 Å) are much longer than some of the van der Waals radii .…”

“…This situation is similar to those observed in the crystal structures of 6 and 10 described above. The S−O, S−C, and Sn−C bond distances as well as the O−S−O and O−S−C bond angles are quite typical of other structurally related sulfonate derivatives. − Another structural feature of the compound is the incorporation of two centrosymmetric [Sn 2 (OH) 2 ] rings in each repeating subunit of the polymer framework. The important bond lengths and bond angles associated with the cyclic ring are as follows: Sn(1)−O(1) 2.112(4), Sn(1)−O(1)#1 2.086(4), Sn(2)−O(7) 2.085(4), Sn(2)−O(7)#2 2.122(4) Å; Sn(1)#1−O(1)−Sn(1) 108.3(2), O(1)#1−Sn(1)−O(1) 71.7(2), Sn(2)−O(7)−Sn(2)#2 107.9(2), O(7)−Sn(2)−O(7)#2 72.1(2)°.…”

Anion Conformation of Low-Viscosity Room-Temperature Ionic Liquid 1-Ethyl-3-methylimidazolium Bis(fluorosulfonyl) Imide

“…Indeed, the C 1 conformer is found in crystals of M + FSI -(M + ) Li + , K + , C 6 H 6 ‚Ag + ), [4][5][6] whereas the C 2 conformer is found in crystals of M + FSI -(M + ) Cs + , CHCl 3 ‚ Ph 3 C + , Ph 3 PH + , and (CH 3 ) 3 Pb + and a series of Xe(II) derivatives). [7][8][9][10][11][12] This evidently indicates that the conformation strongly depends on an ionic environment around the FSIion. Furthermore, the sole C 1 conformer of TFSIis involved in EMI + TFSIcrystals, 13 whereas both C 1 and C 2 conformers are present in the liquid and glassy states.…”

Synthesis of chelating diamido Sn(iv) compounds from oxidation of Sn(ii) and directly from Sn(iv) precursors

“…33 Tin triflates 34 are much less studied than silicon tri- flates but have been used as Lewis-acid catalysts in a handful of organic transformations. 35 There are a number of structurally characterised tin triflates, 12,[36][37][38][39][40][41][42][43] and examples of fourcoordinate tin triflates include [Sn{CH(SiMe 3 ) 2 } 3 OTf ] synthesised by protonation of the corresponding tin hydride using HOTf 44 and another from protonation of a strained [2]ferrocenophane with a CH 2 Sn( t Bu) 2 bridge forming a fourcoordinate tin triflate. 45 Reactions of AgOTf with 12-15 were carried out generating the corresponding tin triflates 16, 17 and 19 but 1 H NMR spectroscopy revealed that reactions to generate 18 also generated other unidentified by-products which could not be separated.…”