Synthese und Struktur von Mo2NCl8 und Mo3N2Cl11Professor Günter Schmid zum 65. Geburtstag gewidmet
作者:Quang Thai Dinh、Markus Richter、Elke Niquet、Joachim Strähle
DOI:10.1002/1521-3749(200208)628:8<1921::aid-zaac1921>3.0.co;2-y
日期:2002.8
The reaction of MoCl5 with Cl3VNCl at 140degreesC in a sealed glass ampoule yields air sensitive black crystals of the mixed valent molybdenum(V,VI) nitride chloride, Mo2NCl8. It crystallizes in the monoclinic space group P2/c with a=996.1(1), b=629.4(1), c=1780.8(3) pm, beta=101.82(2)degrees, and Z=4. The crystal structure consists of dinuclear C-2-symmetrical units [Cl-2(Nequivalent to)Mo(mu(2)-Cl)(3)-Mo(equivalent toN)Cl-2](-) and [Cl4Mo(mu(2)-Cl)MoCl4](+), connected in an alternating sequence by asymmetric nitrido bridges Moequivalent toN-Mo to form chains. The reaction of Cl3VNCl with MoCl3 at 140degreesC affords Mo3N2Cl11, but for the prolonged reaction period, MoNCl3 is observed in addition. Mo3N2Cl11 can also be obtained from MoNCl3 and MoCl5 (2:1) at 140degreesC. It forms orthorhombic, black crystals with the space group Pca2(1) and a=1256.1(1), b=1001.9(1), c=1330.10(5) pm, and Z=4. The structure contains the same dinuclear units [Cl-2(Nequivalent to)Mo(mu(2)-Cl)(3)Mo(equivalent toN)Cl-2](-) as in Mo2NCl8, which in this case are connected with MoCl4+ moieties by asymmetric nitrido bridges Moequivalent toN-Mo forming chains. In Mo2NCl8 the Mo-N distances in the nearly linear nitrido bridges are 167.6(2), and 214.8(2) pm, whereas in case of Mo3N2Cl11 two sets of Mo-N distances of 166,8(4) and 214,0(4) pm as well as 166,9(4) and 211,9(4) pm are observed.