Al(PO2F2)3, Ga(PO2F2)3 und Zn(PO2F2)2 · 2 HOP(O)F2 werden durch Umsetzung von AlCl3, GaCl3, bzw. ZnCl2 mit Difluorophosphorsäure dargestellt. Die physikalischen Eigenschaften und IR‐Spektren der Verbindungen dienen zur Ableitung von Strukturvorschlägen. Für Al(PO2F2)3) und Ga(PO2F2)3 können polymere Strukturen angenommen werden. In Zn((PO2F2)2 2 HOP(O)F2 sind die Säuremoleküle über den terminalen Sauerstoff an das Metallatom gebunden.

[Cl4SbO2P(CH3)2]2 wurde aus SbCl5 und HOP(O)(CH3)2 in CH2Cl2 dargestellt. Die Verbindung kristallisiert monoklin in der Raumgruppe P21/n mit zwei dimeren Einheiten in der Elementarzelle. Die Gitterkonstanten betragen a = 875, b = 1305, c = 923 pm und β = 97,1°. Nach der röntgenographischen Strukturbestimmung (1060 beobachtete, unabhängige Reflexe, R = 3,3%) sind die Sb‐Atome der dimeren Einheiten über OPO‐Brücken der Dimethylphosphinatgruppen zu gewellten Sb2O4P2‐Achtringen der angenäherten Symmetrie C2h verknüpft. Das Schwingungsspektrum (IR, Raman) und die Kernresonanzspektren (31P, 1H) stehen mit dieser Struktur in Einklang.

The complexes cis-[SnCl 4 (H 2 O) 2 ]·2H 2 O (1), [Sn 2 Cl 6 (OH) 2 (H 2 O) 2 ]·4H 2 O (3), and [HL][SnCl 5 (H 2 O)]·2.5H 2 O (4) were isolated from a CH 2 Cl 2 solution of equimolar amounts of SnCl 4 and the ligand L (Lϭ3-acetyl-5-benzyl-1-phenyl-4,5-dihydro-1,2,4-triazine-6-one oxime,C 18 H 18 N 4 O 2 ) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a ϭ 2402.5(1) pm, b ϭ 672.80(4) pm, c ϭ 1162.93(6) pm, β ϭ 93.787(6)°and Z ϭ 8. 4 was found to crystallize monoclinic in the space group P2 1 , with lattice parameters a ϭ 967.38 (5) pm, b ϭ 841 1101.03(6) pm, c ϭ 1258.11(6) pm, β ϭ 98.826(6)°and Z ϭ 2. The cell data for the reinvestigated structures are: [SnCl 4 (H 2 O) 2 ]·3H 2 O (2): a ϭ 1227.0(2) pm, b ϭ 994.8(1) pm, c ϭ 864.0(1) pm, β ϭ 103.86(1)°, with space group C2/c and Z ϭ 4; 3: a ϭ 961.54(16) pm, b ϭ 646.29(7) pm, c ϭ 1248.25(20) pm, β ϭ 92.75(1)°, space group P2 1 /c and Z ϭ 4. Liganden L (Lϭ 3-acetyl-5-benzyl-1-phenyl-4,5,dihydro-1,2,4-triazin-6-on oxim, C 18 H 18 N 4 O 2 ) in CH 2 Cl 2 in Gegenwart von Wasser isoliert. (Kristallstrukturdaten s. Abstract).

IR Spectra, R am an Spectra, Mass Spectra, T riphenyltin D im eth y lp h o sp h in ate T he reactions of (P h 3Sn)20 with P hM eP O C l and w ith P h2P O C l lead to P h 3S n 0 2PM ePh and P h 3S n 0 2PPh2, respectively. Ph3S n 0 2P M e2 has b een p re p a red from the reactio n of (P h 3S n)20 and M e2P 0 2H in toluene. The IR and R am an spectra o f Ph3S n 0 2PM e2, P h 3S nÖ 2PM ePh and P h3S n 0 2P P h2 are found to be consistent w ith polym eric stru ctu res with p entacoordinated tin atom s. The E l mass spectra indicate th a t the principal fragm entation processes of Ph3S n 0 2P R R ' (R R ' = M e2, M ePh, P h2) a p p ear to occur by loss o f phenyl radicals from tin and by elim ination of th e en tire d io rg an o p h o sp h inate group.

Triphenyltin dichloro- and dibromo-phosphate have been prepared from the reactions of (Ph3Sn)2O with POCl3 and with POBr3, respectively. The reactions of POCl3 with R2SnO (R = Me, Et) lead to R2Sn (O2PCl2)2 and R2SnCl2. Diethyltin bis(dichlorophosphate) has been also prepared by the treatment of (Et2ClSn)2O with POCl3. The infrared spectra of Ph3SnO2PX2 (X = Cl, Br) and Et2Sn(O2PCl2)2 are found to be consistent with polymeric structures with pentacoordinated tin atoms in Ph3SnO2PX2 and hexacoordinated tin atoms in Et2Sn(O2PCl2)2. The El mass spectra of R3SnO2PCl2 (R = Me, Ph) and R2Sn(O2PCl2)2 (R = Me, Et) are given and discussed.