Novel butterfly tungsten-osmium carbido cluster Complexes from the reaction of Os3(CO)10(NCME)2 CPW(CO)3(CH2SMe)
Resource
Journal of Cluster Science 6 (2): 289-309
Journal
Journal of Cluster Science
Journal Volume
6
Journal Issue
2
Pages
289-309
Date Issued
1995
Author(s)
Abstract
Condensation of be triosmium acetonitrile complex Os3(CO)10(NCMe)2 with the sulfido complex CpW(CO)3(CH2SMe) in refluxing THF solution produced three sulfur-containing compounds Os3(C0)10)(μ-H)(μ-SMe) (1), Os3(CO)11 [S(Me)CH2W(CO)3Cp] (2) and CpWOs3(CO)12(μ-CH2)(μ-SMe) (3). Clusters 2 and 3 were products involving a 1:1 combination of starting materials and were characterized by X-ray diffraction studies. Crystals of 2 belongs to monoclinic space group P 21/c with a=8.418(2), b = 11.912(2), c = 28.288 Å, β=97.64(2)°, Z=4;RF=0.044, RW,=0.044. Crystal dara far 3: space group P 21/e, a 18.156(4). b=9.255(6), c = 15.347(4) Å. β = 103.49(2)°, Z = 4;RF-=0.047, RW = 0.045. Upon thermolysis in toluene, the methylene cluster 3 released CO and induced C-H bond activation to afford two tetrametallic carbido clusters with formula CPWOS3(CO)9(μ4-C)(μ-H)2(μ-SMe) (4) and CPWOs3(CO)11(μ4-C)(μ-SMe) (5) as the principle products. The first complex possesses a butterfly framework encapsulating a μ4-C ligmd and a μ-SMe ligand linking a W-Os edge, whereas the second product adopts a puckered, cyclic arrangement of WOs3 metal atoms with μ-SMe ligand located on a nonbonding Os-Os vector. Complex 4 crystallizes in monoclinic space group P 21/c with a=15.633(4) Å, b = 8.699 (3) Å, c=15.422(4) Å, β=93.12(2)=°, Z=4, R=0.036, RW=0.034 for 2780 observed reflections. Crystal data for 5: space group P nma, a=14.542(3), b=13.710(6), c=11.758(3) Å. Z=4, RF =0.038, RW = 0.037 for 1826 observed reflections. A variable temperature1H NMR study was also presented to demonstrate the solution fluxionality of 5. © 1995 Plenum Publishing Corporation.
Type
journal article
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