Synthesis of the first fluoro(phosphanyl)- and diphosphanyl-stannanes and surprising formation of [P(SnMe3)4]+ SiF5-.
Monophosphanylation of the difluorostannane Is2SnF2 (Is = 2,4,6-triisopropylphenyl) with Si(PH2)4 furnishes the first isolable fluoro(phosphanyl)stannane Is2Sn(F)PH2 1, which readily undergoes unique SiO2-assisted decompostion to [Is2Sn(PH)]2 2 and HF, while further phosphanylation of 1 leads to the remarkably stable diphosphanylstannane Is2Sn(PH2)2 3; the latter reacts with Me3SnF at the glass-wall to give the first perstannylphosphonium pentafluorosilicate [P(SnMe3)4]+ SiF5- 4.
Synthese der Stannatetraphospholane (tBuP)4SnR2 (R = tBu, nBu, C6H5) und (tBuP)4Sn(Cl)nBu Molekül‐ und Kristallstruktur von (tBuP)4Sn(tBu)2
Bei der Reaktion zwischen dem Diphosphid K2[tBuP-(tBuP)2-PtBu] 4 und den Halogenstannanen (tBu)2SnCl2, (nBu)2SnCl2, (C6H5)2SnCl2 bzw. nBuSnCl3 im Molverhaltnis 1 : 1 findet eine [4 + 1]-Cyclokondensationsreaktion statt, bei der die Stannatetraphospholane (tBuP)4SnR23b–3d bzw. (tBuP)4Sn(Cl)nBu 3 e mit dem binaren Funfringgerust P4Sn gebildet werden. Von 3 b wurde eine Einkristallstrukturanalyse durchgefuhrt; das Funfringgerust zeigt eine planare Konformation. Die Verbindungen 3 b–3 e wurden Massen- und NMR-spektroskopisch charakterisiert; 3 b–3 d liefern im 31P{1H}-NMR-Spektrum ein AA′MM′-(AA′MM′X)-, 3 e dagegen ein ABCD- (ABCDX)-Spinsystem. 
 
 
 
Synthesis of the Stannatetraphospholanes (tBuP)4SnR2 (R = tBu, nBu, C6H5) and (tBuP)4Sn(Cl)nBu Molecular and Crystal Structure of (tBuP)4Sn(tBu)2 
 
 
 
The reaction of the diphosphide K2[tBuP-(tBuP)2-PtBu] 4 with the halogenostannanes (tBu)2SnCl2, (nBu)2SnCl2, (C6H5)2SnCl2 or nBuSnCl3 in a molar ratio of 1 : 1 leads via a [4 + 1]-cyclocondensation reaction to the stannatetraphospholanes (tBuP)4SnR23 b–3 d and (tBuP)4Sn(Cl)nBu 3 e, respectively, with the binary 5-membered P4Sn ring system. 3 b was characterized by a single crystal structure analysis; the 5-membered ring exists in a planar conformation. The compounds 3 b–3 e were identified by NMR and also by mass spectroscopy; the 31P{1H}-NMR spectra of 3 b–3 d showed an AA′MM′ (AA′MM′X), 3 e on the other hand an ABCD (ABCDX) spin system.
Zur struktur einiger cyclischer Diorganylzinn—Stickstoff-Verbindungen
Abstract Two new cyclostannazanes, (t-Bu 2 SnN-t-Bu) 2 and (t-Bu 2 SnNSO 2 Me) 2 have been synthesized. Their structures have been determined by X-ray diffraction together with that of (t-Bu 2 SnNH) 3 . All three compounds contain planar four- or six-membered tin—nitrogen rings. The coordination of the nitrogen atoms in (t-Bu 2 SnN-t-Bu) 2 is almost planar, whereas that of the others is distorted trigonal pyramidal. In the four-membered rings the angles at the tin atoms are remarkably small.