Structural characterization of paramagnetic, triangulo niobium clusters, Cp'/sub 3/Nb/sub 3/Cl/sub 3/(/mu//sub 2/-Cl)/sub 3/(/mu//sub 3/-O)(/mu//sub 3/-X) (X = OH, Cl)
The Nb(III) complex (Cp'Nb(CO)/sub 2/Cl/sub 2/)/sub 2/ (1, Cp' = C/sub 5/H/sub 4/Me) undergoes decarbonylation in refluxing THF to give a dark brown paramagnetic compound believed to be Cp'/sub 3/Nb/sub 3/Cl/sub 6/(/mu//sub 3/-O) (2). Compound 2 reacts with atmospheric oxygen to produce Cp'/sub 3/Nb/sub 3/Cl/sub 3/(/mu//sub 2/-Cl)/sub 3/(/mu//sub 3/-O)(/mu//sub 3/-OH) (3) and with chlorinated hydrocarbons to form Cp'/sub 3/Nb/sub 3/Cl/sub 3/(/mu//sub 2/-Cl)/sub 3/(/mu//sub 3/-O)(/mu//sub 3/-Cl) (4). Compounds 3 and 4 are paramagnetic. X-ray structure determinations show that each of these clusters has one short Nb-Nb distance of ca. 2.92 /angstrom/ corresponding to a Nb-Nb bond and two long Nb/center dot//center dot//center dot/Nb distances near 3.28 (3) or 3.39 /angstrom/ (4). The Nb/sub 3/ triangle is bridged by Cl atoms along each edge and is capped by a /mu//sub 3/-oxo ligand and a /mu//sub 3/-hydroxo (3) or /mu//sub 3/-chloro ligand (4) on opposite sides of the Nb/sub 3/ plane. Terminal Cp and Cl ligands complete the coordination sphere about each Nb atom. Crystal data: for 3, a = 7.210 (2) /angstrom/, b = 26.097 (7) /angstrom/, c = 12.518 (3) /angstrom/, /beta/ = 94.18 (2)/degree/, space group P2/sub 1//n, Z = 4, V = 2349 /angstrom//sup 3/, /rho//sub calcd/ = 2.06 g/mL, R = 0.039 and R/sub w/ = 0.054 on 2551 reflections with I > 3/sigma/(I); for 4, a = 7.620 (1) /angstrom/, b = 15.108 (4) /angstrom/, c = 21.670 (6) /angstrom/, /alpha/ = 87.45 (2)/degree/, /beta/ = 93.68 (2)/degree/, /gamma/ = 104.01 (2)/degree/, space group P1, Z = 4, V = 2414 (1) /angstrom//sup 3/, /rho//sub calcd/ = 2.01 g/mL, R = 0.065 and R/sub w/ = 0.055 on 2424 reflections with I > 3/sigma/(I). 6 references, 3 figures, 4 tables.
- Research Organization:
- Univ. of Michigan, Ann Arbor (USA)
- OSTI ID:
- 5762095
- Journal Information:
- Inorg. Chem.; (United States), Vol. 27:18
- Country of Publication:
- United States
- Language:
- English
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