Cp₃Zr(acetonitrile)⁺: Structure of an Electron‐Rich Organometallic d⁰‐Cation

Abstract

~ ~~~~~~~The organometallic salt [Cp,Zr(N=C-CH,)

CH3CN: X-ray structural investigation of a unique single crystal. β → α phase transition and crystal structure

“…The structure determination of the form is in good agreement with the structures determined by Barrow (1981) and Brackmeyer et al (1997). Fig.…”

“…form of CH 3 CN, structurally depicted by Barrow (1981). This latter work was performed using a Weissenberg camera and Cu K radiation, the crystal being cooled and maintained at 215 K. Brackmeyer et al (1997) con®rmed this work in their single-crystal study at 208 K on an automatic diffractometer. On obtaining such a good crystal after the transition, it was decided to take the opportunity to re®ne its structure, in order to facilitate comparisons with the form and to understand the ongoing molecular mechanism.…”

“…Barrow (1981) studied the form at 215 K, using equi-inclination multiple-®lm packing methods (Cu K), the acetonitrile being sealed in a Lindeman capillary. Brackmeyer et al (1997) studied the form at 208 K, using a single crystal grown in situ on a diffractometer by a zone-melting technique. Antson et al (1987) determined the approximate structure of the deuterated acetonitrile using a C3v molecular model and neutron diffraction techniques.…”

Expedient Syntheses of Neutral and Cationic Au(I)–NHC Complexes

“…Bond angles C-Au-N indicated near-linear structures and bond lengths C-Au and Au-N showed little variation ( Table 7). As previously observed for the PF6-based analogous compound [Au(IPr)(NCCH3)][PF6], 4 the N≡C bonds in the coordinated acetonitrile molecules were slightly shorter than in non-coordinated acetonitrile (1.141 Å), 40 consistent with the measured increases in stretching frequencies (Table 6). -d) at 50% probability.…”

cis-Bis(acetonitrile)tetrachlorotin(IV) acetonitrile solvate,cis-tetrachlorobis(propiononitrile)tin(IV) propiononitrile solvate,cis-tetrachlorobis(isobutyronitrile)tin(IV),cis-tetrachlorobis(cyclohexanecarbonitrile)tin(IV) andcis-tetrachlorobis(o-toluonitrile)tin(IV), all determined atca150 K

“…The same is true of the NÐC distances [1.126 (6)±1.1428 (18) A Ê ]. These values are similar to those reported recently for a free acetonitrile ligand [1.141 (2) A Ê ; Brackemeyer et al, 1997], which implies that the numerous suggestions of a dependence of this bond on coordination, admittedly contingent on the nature of the metal, perhaps should be subject to closer scrutiny and that libration corrections may be necessary.…”