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UBC Theses and Dissertations
The chemistry of group 6 and 7 transition metal organometallic nitrosyl complexes Kolthamer, Brian William Stirling
Nitrosyl chloride exhibits a number of different reaction modes in its reactions with monomeric and dimeric neutral carbonyl complexes of transition metals. From its reaction with [CpCr(CO)₃]₂ under controlled conditions, the organometallic compounds CpCr (CO)₂(NO) , CpCr(NO)₂Cl, [CpCrCl2]2, and [CpCr (NO) Cl₂]₂ can be obtained. In contrast.,, the analogous [CpM(CO)₃] ₂ (M — Mo or W) compounds react with C1N0 to produce CpM(CO)3Cl and CpM(NO)₂Cl in comparable yields. The (arene)M(CO)₃ (M = Mo or W) compounds form the polymeric [M(NO)2Cl2]n species via labile M (CO)₂(NO) 2Cl₂ intermediates under identical experimental conditions. Possible pathways leading to the formation of all products are presented. Trithiazyl trichloride, N₃S₃Cl₃, introduces the thionitrosyl group onto a metal centre during the reaction. Na[CpCr (CO)₃] + (1/3) N₃S₃3Cl₃ • CpCr (CO)₂(NS) An x-ray crystallographic analysis of this complex shows that the thionitrosyl group coordinates essentially linearly to the chromium via the nitrogen atom. A second product formed in this reaction, Cp₂Cr₂ (CO)₄S, possesses a novel Cr-S-Cr linkage which is linear, short, and chemically inert The cations, [(RC₅H₄)Mn(CO)₂(NO)] + (R = H or Me) react with I in acetone at room temperature to produce (RC₅H₄)Mn(CO)₂(NO)I. These species have very labile CO ligand which are readily displaced by Lewis bases to produce (RC₅H₄) - Mn(L) (NO)I [R = H, L = PPh₃ or P(OPh)₃; R = Me, L = PPh3, P(OPh)₃, or P(C₆H₁₁:L)₃]. The reactions of Br-, Cl⁻, and NO₂⁻ with [(RC₅H₄)Mn(CO)2(NO)]⁺ produce the unusual bimetallic compounds (RC₅H₄)₂Mn₂ (NO) ₃X (R == H or Me; X = Cl, Br, or N₂) The compound [CpCr(NO)2]2 abstracts all of the chlorine ligands from SnCl₄, MCl₂ (M = Hg, Sn, or Pb), CpFe-(CO)₂Cl, and Mn(CO)₅Cl in. refluxing thf to form CpCr(NO)₂Cl. The other products are the metals (M), [CpFe(CO)₂]₂, and Mn₂(CO)₁₀, respectively. The chromium dimer also abstracts halogen from vic-dihaloalkanes to produce the corresponding alkenes in good yields.
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