ISSN:
0044-2313
Keywords:
Zinc cluster
;
Cadmium cluster
;
crystal cluster
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Reactions of Zinc and Cadmium Halides with Tris(trimethylsilyl)phosphane and Tris(trimethylsilyl)arsane The Crystal Structures of [ZnI2{P(SiMe3)3}]2,[CdI2{P(SiMe3)3}]2,[NnBu4]2[Zn6I6(PSiMe3)4(C4H8O)2] · C6H6,[NnBu4]2[Cd4I8{P(SiMe3)2}2],[Zn4Cl4{P(SiMe3)2}4(MeCN)2],[Zn4Cl4{As(SiMe3)2}4(MeCN)2] and [Zn10Cl12(PSiMe3)4(PEt2Ph)4]ZnI2 and CdI2 react with P(SiMe3)3 in diethylether resp. DME to the binuclear complexes [MI2{P(SiMe3)3}]2 (M = Zn 1, Cd 2). Further reaction of 1 with NnBu4I in THF leads to the formation of [NnBu4]2[Zn6I6(PSiMe3) 4(C4H8O)2]C6H6 3. 2 reacts with NnBu4I in THF to [NnBu4]2[Cd4I8{P(SiMe3) 2}2] 4.The reactions of ZnCl2 with P(SiMe3)3 resp. As(SiMe3)3 in MeCN at 0°C lead in a first step to the formation of the tetranuclear [Zn4Cl4{E(SiMe3)2}4(MeCN) 2] (E = P 5, As 6). The addition of the tertiary phosphine PEt2Ph to the reaction solution of ZnCl2 and P(SiMe3)3 in DME and subsequent layering with hexane results in the formation of [Zn10Cl12(PSiMe3)4(PEt2Ph) 4] 7.The structures of 1-7 were obtained by X-ray single crystal structure analysis (1: space group P212121 (Nr. 19), Z = 4, a = 1189.1 (2) pm, b = 1390.7(3) pm, c = 2550.7(5) pm; 2: space group P212121 (Nr. 19), Z = 4, a = 1499.5(3) pm, b = 1588.8(3) pm, c = 1813.5(4) pm; 3: space group Ibca (Nr. 73), Z = 8, a = 2365.5(5) pm, b = 2519.6(5) pm, c = 3118.7(6) pm; 4: space group Pna21 (Nr. 33), Z = 4, a = 1943.7(4) pm, b = 2032.9(4) pm, c = 2029.3(4) pm; 5: space group C2/c (Nr. 15), Z = 4, a = 2269.4(5) pm, b = 1471.5(3) pm, c = 1792.0(4) pm, β = 93.79(3)°; 6 space group C2/c (Nr. 15), Z = 4, a = 2262.4(5) pm, b = 1494.2(3) pm, c = 1801.1(4) pm, β = 90.30(3)°; 7: space group I41/a (Nr. 88), Z = 4, a = 2702.8(4) pm, b = 2702.8(4) pm, c = 1240.4(3) pm).
Notes:
ZnI2 und CdI2 reagieren mit P(SiMe3)3 in Diethylether bzw. DME zu den Zweikernkomplexen [MI2{P(SiMe3)3}]2 (M = Zn 1, Cd 2). 1 reagiert mit NnBu4I in THF unter Bildung von [NnBu4]2[Zn6I6(PSiMe3) 4(C4H8O)2]· C6H6 3. Dagegen erhält man aus 2 mit NnBu4I in THF den ionischen Cluster [NnBu4]2[Cd4I8{P(SiMe3) 2}2] 4.Die Reaktionen von ZnCl2 mit P(SiMe3)3 bzw. As(SiMe3)3 führen in MeCN bei 4°C in einer ersten Stufe zur Bildung der vierkernigen Zinkkomplexe [Zn4Cl4{E(SiMe3)2}4(MeCN) 2](E = P 5, As 6).Unter Verwendung eines tertiären Phosphans, PEt2Ph, lassen sich aus der Reaktionslösung von ZnCl2 mit P(SiMe3)3 in DME farblose kristalle des Mehrkernkomplexes [Zn10Cl12(PSiMe3)4(PEt2Ph) 4] 7 isolieren.Die Strukturen von 1-7 konnten durch Einkristall-Röntgenstrukturananlyse aufgeklärt werden. (1: Raumgruppe P212121 (Nr.19), Z = 4, a = 1189,1(2) pm, b = 1390,7(3) pm, c = 2550,7(5) pm; 2: Raumgruppe P212121 (Nr.19), Z = 4, a = 1499,5(3) pm, b = 1588,8(3) pm, c = 1813,5(4) pm; 3: Raumgruppe Ibca (Nr.73), Z = 8, a = 2365,5(5) pm, b = 2519,6(5) pm, c = 3118,7(6) pm; 4: Raumgruppe Pna21 (Nr.33), Z = 4, a = 1943,7(4) pm, b = 2032,9(4) pm, c = 2029,3(4) pm; 5: Raumgruppe C2/c (Nr.15), Z = 4, a = 2269,4(5) pm, b = 1471,5(3) pm, c = 1792,0(4) pm, β = 93,79(3)°; 6: Raumgruppe C2/c (Nr.15), Z = 4, a = 2262,4(5) pm, b = 1494,2(3) pm, c = 1801,1(4) pm, β = 90,30(3)°; 7: Raumgruppe I41/a (Nr.88), Z = 4, a = 2702,8(4) pm, b = 2702,8(4) pm, c = 1240,4(3) pm).
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.199762301120
