Single crystal X‐ray diffraction analyses of LSn(OCH2CH2)2NR [1, R = Me, L = lone pair; 2, R = Me, L = W(CO)5; 3, R = t‐Bu, L = W(CO)5] reveal these compounds to be dimeric and cis‐configurated. The dimerization is realized by intramolecular O→Sn interactions to give four‐membered Sn2O2‐rings. In addition, there are intramolecular N→Sn interactions ranging in between 2.356(5) (2) and 2.549(4) Å (3).
Über erste Synthesen von Trifluormetylkomplexen des Platins durch Fluorierung von Cyanoplatinaten wird berichtet. Die Fluorierung des Tetracyanoplatinates(II), K2[Pt(CN)4], und Hexacyanoplatinates(IV), K2[Pt(CN)6], mit ClF in wasserfreier HF führt nach Aufarbeitung der Produkte zu K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O. Der Aufbau des Salzes ist durch eine Röntgenstrukturanalyse abgesichert, P21/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R1 = 0.0326 (I > 2σ(I)). Bei der Reaktion von [Bu4N]2[Pt(CN)4] mit ClF in CH2Cl2 entstehen hauptsächlich cis‐[Bu4N]2[PtCl2(CF3)4] und fac‐[Bu4N]2[PtCl3(CF3)3], dagegen führt die Umsetzung von [Bu4N]2[Pt(CN)6] mit ClF in CH2Cl2 zu cis‐[Bu4N]2[PtX2(CF3)4], [Bu4N]2[PtX(CF3)5] (X = F, Cl) und [Bu4N]2[Pt(CF3)6]. In den Produkten [Bu4N]2[PtXn(CF3)6‐n] (X = F, Cl, n = 0—3) lassen sich mit (CH3)3SiCl und (CH3)3SiCN bei 50 °C die Fluoroliganden gegen Chloro‐ bzw. Cyanoliganden austauschen. Bei weiterem Erwärmen werden außerdem die Trifluormethylliganden stufenweise gegen Chloro‐ bzw. Cyanoliganden ersetzt, wobei sich intermediär CF2Cl‐ bzw. CF2CN‐Liganden bilden. Der Aufbau der neuen Trifluormethylplatinate wird durch die Analyse der 195Pt‐ und 19F‐NMR‐Spektren eindeutig belegt.
The syntheses of the tin compounds [LSn]2 (2), spiro‐L2Sn (3), [LSnW(CO)5]2 (4), [LSnBr2]2 (5), spiro‐L2Sn·SnBr4 (6) and LSn[OC(O)Ph]2 (8), where L = MeN(CH2CMe2O)[(S)‐CH(Me)‐(R)‐CH(Ph)O], and (Ph4P)2SnBr6 (7) are reported. The compounds were characterized by elemental analysis, multinuclear NMR spectroscopy including 119Sn cross polarisation–magic angle spinning NMR (CP–MAS) (2, 3–6), electrospray ionization mass spectrometry (2–4) and single crystal X‐ray diffraction analysis (2, 2·C7H8, 3a, 3b, 4·C7H8, 5, 6·C7H8, 7).
Extending the classical reactivity pattern of tin: Elemental tin reacts with alcohols to give, depending on the identity of the alcohol and the reaction conditions, a variety of tin alcoholates and tinoxo clusters (see scheme).
The syntheses of new potentially tetradentate ligands of the type RN(CH 2 CMe 2 OH) 2 (1, R = Me 2 NCH 2 CH 2 ; 2, R = MeOCH 2 CH 2 ), their tin(II) derivatives RN(CH 2 CMe 2 O) 2 Sn (3, R = Me 2 NCH 2 CH 2 ; 4, R = MeOCH 2 CH 2 ), the pentacarbonyltungsten complexes RN(CH 2 CMe 2 O) 2 SnW(CO) 5 (5, R = Me 2 NCH 2 CH 2 ; 6, R = MeOCH 2 CH 2 ) and their oxidation products with bromine, RN(CH 2 CMe 2 O) 2 SnBr 2 (7, R =
[a]Me 2 NCH 2 CH 2 ; 8, R = MeOCH 2 CH 2 ), are reported. The compounds were characterized by multinuclear NMR spectroscopy, elemental analysis, electrospray ionization mass spectrometry and single-crystal X-ray diffraction analysis. DFT calculations on compounds 3, 7 and 8 suggest the preference of dimeric over monomeric structures.Scheme 4. Synthesis of the compounds 5-8.
The syntheses and molecular structures of the intramolecularly coordinated tin(II) compounds {CH(2)N(Me)CH(Me)CH(Ph)O}(2)SnL (2, L = lone pair; 4, L = W(CO)(5); 5, L = Cr(CO)(5)) and of the related hydroxido-substituted tin(IV) compound [{CH(2)N(Me)CH(Me)CH(Ph)O}(2)Sn(OH)](2)O, 6a, are reported. Also reported are the molecular structures of the enantiopure N,N'-ethylenebis-(1R,2S)-ephedrine, {CH(2)N(Me)CH(Me)CH(Ph)OH}(2) (1), and its hydrobromide {CH(2)N(Me)CH(Me)CH(Ph)OH}(2)·HBr (1a).
The synthesis of the intramolecularly coordinated stannylenes and their transition-metal complexes of the type RN(CH 2 CMe 2 O) 2 SnL [1: L = lone pair, R = Me; 2: L = lone pair, R = n-octyl; 5: L =W(CO) 5 , R = Me; 6: L = Cr(CO) 5 , R = Me; 7: L =W(CO) 5 , R = n-octyl; 8: L = Fe(CO) 4 , R = Me], and of the tin(IV) compounds RN(CH 2 CMe 2 O) 2 SnBr 2 (9: R = Me), [a] 3463 [MeN(CH 2 CMe 2 O) 2 SnBr 2 ] 2 ·SnBr 2 (OH) 2 (10) and spiro-[RN(CH 2 CMe 2 O) 2 ] 2 Sn (3: R = Me; 4: R = n-octyl) is reported. The compounds were characterized by elemental analyses, 1 H, 13 C, 119 Sn, and 119 Sn magic-angle spinning (5, 6) NMR spectroscopy, electrospray mass spectrometry, and singlecrystal X-ray diffraction analysis. exhibit superior crystallization properties. They also enabled the isolation of an unprecedented trinuclear Sn-O cluster. www.eurjic.org 3469 119 Sn MAS Spectroscopy: The 119 Sn MAS NMR spectra were recorded with a Bruker Avance III 400 spectrometer using cross polarization and high-power proton decoupling [conditions: 3.7 μS (90°) pulse, 2 ms contact time, 10 s recycle delay]. For compounds Eur.
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