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Synthesis, Crystal Structure, and Bonding of (PCl4)2[Mo2Cl10], the First Compound in Mo–P–Cl System

✍ Scribed by G. V. Khvorykh; S. I. Troyanov; A. I. Baranov; A. A. Serov

Publisher
John Wiley and Sons
Year
1998
Tongue
German
Weight
88 KB
Volume
624
Category
Article
ISSN
0372-7874

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✦ Synopsis

An ampule reaction between Mo and PCl 5 at 200 °C yielded (PCl 4 ) 2 [Mo 2 Cl 10 ], the first ternary compound in Mo±P±Cl system. Single crystal X-ray diffraction gave a triclinic unit cell: a = 6.870(1), b = 8.892(2), c = 9.423(2) A Ê , α = 100.24(2), b = 95.55(2), c = 96.12(2)°(V = 559.3(2) A Ê 3 , Z = 1, sp. gr. P1, wR 2 = 0.0575 and R 1 = 0.0279. The ionic compound is built from edge sharing bioctahedra [Mo 2 Cl 10 ] 2± and two tetrahedra PCl 4 + . The averaged Mo±Cl b distance, 2.503(1) A Ê , is longer than the Mo±Cl t distance, 2.33(2) A Ê . The Mo ´´´Mo distance, 3.77 A Ê , indicates the absence of a direct Mo±Mo interaction. Semiempirical and ab initio calculations showed the possibility for [Mo 2 Cl 10 ] 2± to exist with long and short Mo to Mo distances, the letter corresponding to the Mo±Mo bond.

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