Triethylphosphanimin-Komplexe der Acetate von Kupfer(II) und Zink. Kristallstrukturen von [Zn(O2C–CH3)2(HNPEt3)], [Cu5(O2C–CH3)10(HNPEt3)2] und [Cu(O2C–CH3)2(HNPEt3)2]

✍ Scribed by H. Ackermann; G. Geiseler; K. Harms; R. Leo; W. Massa; F. Weller; K. Dehnicke

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: German
• Weight: 224 KB
• Volume: 625
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(199909)625:9<1500::aid-zaac1500>3.0.co;2-t

✦ Synopsis

Inhaltsu È bersicht. Die Titelverbindungen entstehen aus den wasserfreien Acetaten von Zink und Kupfer(II) mit Trimethylsilyl-triethylphosphanimin, Me 3 SiNPEt 3 , in Gegenwart von Wasser in Dichlormethan als farblose (1), blaugru È ne (2) bzw. blaue (3) Einkristalle, die IR-spektroskopisch und durch Kristallstrukturanalysen charakterisiert werden.

[Zn(O 2 C±CH 3 ) 2 (HNPEt 3 )] (1): Raumgruppe P 4 2 1 c, Z = 8, Gitterabmessungen bei ±83 °C: a = b = 1709,6(2); c = 982,4(1) pm, R = 0,0551. 1 hat eine polymere Kettenstruktur, in der die Zink-Atome u È ber die O-Atome einer der beiden Acetato-Gruppen l 2 -verbru È ckt sind, wa È hrend die zweite Acetato-Gruppe und das Phosphanimin terminal gebunden sind.

[Cu 5 (O 2 C±CH 3 ) 10 (HNPEt 3 ) 2 ](2 ´4 CH 2 Cl 2 ): Raumgruppe P2 1 /c, Z = 8, Gitterabmessungen bei ±80 °C: a = 1761,18( 13); b = 4074,5(2); c = 1733,34(15) pm; b = 91,383(10)°, R = 0,0413. 2 besteht aus den beiden Struktureinheiten [Cu 2 (O 2 C±CH 3 ) 4 ] und [Cu 3 (O 2 C±CH 3 ) 6 (HNPEt 3 ) 2 ], die u È ber zwei der Acetato-Gruppen der Cu 3 -Einheiten entlang der kristallographischen a-Achse zu drei kristallographisch unabha È ngigen polymeren Stra È ngen verbunden sind. [Cu(O 2 C±CH 3 ) 2 (HNPEt 3 ) 2 ] (3): Raumgruppe P2 1 /n, Z = 2, Gitterabmessungen bei 20 °C: a = 695,49(8); b = 1217,85(10); c = 1380,05(7) pm; b = 96,451(7)°, R = 0,0291. 3 bildet monomere, zentrosymmetrische Moleku È le mit quadratisch planarer Umgebung an den Cu-Atomen. Triethylphosphanimine Complexes of the Acetates of Copper(II) and Zinc. Crystal Structures of [Zn(O 2 C±CH 3 ) 2 (HNPEt 3 )], [Cu 5 (O 2 C±CH 3 ) 10 (HNPEt 3 ) 2 ], and [Cu(O 2 C±CH 3 ) 2 (HNPEt 3 ) 2 ]

Abstract. The title compounds originate from the anhydrous acetates of zinc and copper(II) with trimethylsilyl-triethylphosphanimine, Me 3 SiNPEt 3 , in the presence of water in dichloromethane. They form colourless (1), bluish-green (2), and blue (3), respectively, single crystals, which were characterized by IR spectroscopy and by crystal structure analyses.

[Zn(O 2 C±CH 3 ) 2 (HNPEt 3 )] (1): Space group P 4 2 1 c, Z = 8, lattice dimensions at ±83 °C: a = b = 1709.6(2), c = 982.4(1) pm, R = 0.0551. 1 has a polymeric chain structure in which the zinc atoms are l 2 -bridged via the oxygen atoms of one of the two acetato groups, while the second acetato group and the phosphanimine are bonded terminally.

[Cu 5 (O 2 C±CH 3 ) 10 (HNPEt 3 ) 2 ](2 ´4 CH 2 Cl 2 ): Space group P2 1 /c, Z = 8, lattice dimensions at ±80 °C: a = 1761.18( 13), b = 4074.5(2), c = 1733.34(15) pm, b = 91.383(10)°, R = 0.0413. 2 consists of the two structural units [Cu 2 (O 2 C±CH 3 ) 4 ] and [Cu 3 (O 2 C±CH 3 ) 6 (HNPEt 3 ) 2 ], which are connected via two of the acetato groups of the Cu 3 -unit along the crystallographic a-axis to form three crystallographically independent polymeric strands. [Cu(O 2 C±CH 3 ) 2 (HNPEt 3 ) 2 ] (3): Space group P2 1 /n, Z = 2, lattice dimensions at 20 °C: a = 695.49(8), b = 1217.85(10), c = 1380.05(7) pm, b = 96.451(7)°, R = 0.0291. 3 forms monomeric, centrosymmetric molecules with a square planar environment at the Cu atoms.