T h e cis-cyclooctene a n d norbornene complexes of AuCl, AuC1(cis-CgH14) (1) a n d AuCl (C,H,,) (2), respectively, have been prepared from t h e reaction of AuCl(C0) with t h e corresponding olefin a t room temperature by a CO displacement reaction. Gas volumetric equilibrium data on t h e reaction between AuCl(C0) and norbornene show that the formation of the olefin complex is favored at atmospheric pressure of carbon monoxide. T h e constant of t h e equilibrium AuCl(C0) + norbornene s AuCl(norbornene) + CO is K = 4 f 1 at 21.5 "C. No CO was found t o be displaced from AuCl(C0) with cyanoolefins. T h e crystal structure of 1 has been solved by X-ray diffraction methods. For 2, only t h e crystal d a t a and a structure with insufficient resolution were obtained. T h e crystal data at 190 K are as follows: 1, a = 23.115 (4) A, b = 5.419 (3) A, c = 7.356 (2) A, 2 = 4, orthorhombic, space group P c~2~, R = 0.037; 2, a = 5.697 (2) A, b = 20.24 (1) A, c = 6.620 (2) A, 2 = 4, orthorhombic, space group Ama2, R = 0.085. T h e gold atom presents t h e expected linear geometry, considering t h e olefin as a monodentate ligand.
AbstractReNCl2(PMe2Ph)3 reacts as a Lewis base and with BCl3 forms a nitrido bridge between Re and B. The resulting complex Re(NBCl3)Cl2(PMe2Ph)3 crystallizes orthorhombic in the space group Pn21 a with Z = 4. In the complex each Re atom has six nearest neighbours in an almost octahedral arrangement with the NBCl3 group being trans to one of the Cl ligands. The difference between the two Re-Cl bond lengths (239,4 and 243,9 pm) indicates a weak trans effect of NBCl3. The linear bridge Re≡N-B has bonding distances of Re-N = 172,8 and N-B = 153 pm. Bonding of BCl3 by the nitrido ligand causes a small increase in the Re-N bond distance.
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