The selective complexation of adamantane nitriles by tungsten pentacarbonyl

Abstract

Adamantyl-l,3,4-oxathiazol-2-one is usually prepared as a mixture with 1 -adamantanecarbonitrile. To separate these two compounds the mixture is reacted with thf.W(CO),, which selectively forms a complex with the nitrile. The resulting mixture can then be readily separated into pure compounds by sublimation. Characterization data are presented, including the X-ray crystal structure of the nitrile complex, which can be prepared directly from the reaction of the adamantyl nitrile and thf.W(CO),. (Crystal data for C16H,,N05W: orthorhombic, space group Prncn, a = 10.5869(19) A, b = 14.0622(22) A, c = 23.342(4) A, V = 3475.0(11) A' , Z = 8, K = 0.042.) The nitrile can be recovered from the complex by reaction with P(C6H,), followed with separation by sublimation. The reaction of the related 1-cyano-3-(1,3,4-oxathiazo1-2-on-5-y1)-adamantane with thf.W(CO), yields a complex in which the site of coordination is shown spectroscopically to be the nitrile moiety. Semi-empirical calculations at the PM3 level indicate that the oxathiazolone heterocycle may be a poor ligand due to the influence of the exo-and endo-cyclic oxygen atoms.Key words: oxathiazolone, nitrile, tungsten, complexation, selectivity, adamantane.Resume : L'adamantyl-l,3,4-oxathiazol-2-one est gkntralement prkpar6.e sous la forme d'un melange avec l'adamantane-lcarbonitrile. Pour stparer ces deux composts, on fait rtagir le mtlange avec du thf.W(CO), qui forme sklectivement un complexe avec le nitrile. Le mtlange qui en rksulte peut alors &tre sCpark facilement en composCs purs par sublimation. On prCsente des donnCes de caractkrisation, y compris la structure cristalline par diffraction des rayons X du complexe avec le nitrile qui peut &tre prCparC directement par rkaction de l'adamantylnitrile avec du thf.W(CO),. Les donnkes cristallines pour Cl,Hl,NO,W : orthorhombique, groupe d'espace Pmcn, a = 10,5869(19), b = 14,0622 (22)

Experimental and Computational Studies of Binding of Dinitrogen, Nitriles, Azides, Diazoalkanes, Pyridine, and Pyrazines to M(PR3)2(CO)3 (M = Mo, W; R = Me, iPr).

“…This is consistent with the backbonding being enhanced by the electron-withdrawing fluorines. The M−N bond distances for the complexes with nitrile adducts are consistent with literature values: 2.190(5) Å in fac -W(dppm)(CO) 3 (CH 3 CN), 2.227(12) and 2.204(12) Å for two separate forms of W(CO) 5 (AdCN), and 2.21 Å in W(CO) 3 (CH 3 CN) 3 …”

Synthesis and photochemistry of free base and zinc tetraaryl porphyrins mono-substituted with tungsten pentacarbonyl via a pyridine linker

“…The IR spectroscopic data agree with literature values for C 4v M(CO) 5 (substituted-pyridine) complexes (Table 1). 20,23,25, 26 The Scheme 1 The syntheses of 3a, 3b, W(CO) 5 3a and W(CO) 5 3b. Scheme 2 Compounds 4a, 4b, W(CO) 5 4a, W(CO) 5 4b, 5, 6 and 7.…”

(Acetonitrile-κN)pentacarbonyltungsten(0)

“…For other structures with an (alkyl nitrile-N)pentacarbonyltungsten(0) fragment, see: Darensbourg et al (1992); Reibenspies et al (1994); Jefford et al (1996). For structures with conjugated nitriles, see: Fischer et al (1993); Helten et al (2010) and for structures with nitriles that are part of an organometallic complex, see: Busetto et al (1992); Duclos et al (1999); Tang et al (1999); Trylus et al (1999); Cordiner et al (2006).…”

“…E67, m772 When the present molecular structure of [W(CH 3 CN)(CO) 5 ] is compared to other literature examples of (nitrile-κN)pentacarbonyltungsten(0) compounds, surprisingly no significant variations in bond lengths can be observed within the metal-ligand bonds despite different electronic and steric properties of the nitriles used. Related crystal structures reported include the W(CO) 5 adducts of alkylnitriles (Reibenspies et al, 1994;Jefford et al, 1996), conjugated nitriles (Fischer et al, 1993;Tang et al, 1999;Cordiner et al, 2006;Helten et al, 2010), α-metal-substituted alkyl nitriles (Busetto et al, 1992;Trylus et al, 1999) as well as deprotonated 2,3,4-tricyanopent-2-enedinitrile (Duclos et al, 1999).…”