- 作者: 游源祥 ; 李錦祥 ; 彭旭明
- 作者服務機構: 台灣大學化學系
- 中文摘要: The monomeric octa-aza bis-.alpha.-diimine macrocyclic complex [ Co/sup II/(C/sub 10/H/sub 20/N/sub 8/)(H/sub 2/O)/sub 2/ ] (ClO/sub 4/)/sub 2/I, undergoes various reactions on the macrocyclic ligand. Reaction of complex I with triethylamine in double molar proportions, followed by slow aerial oxidation, produces a molecular dimeric complex [ Co/sup II/(C/sub 10/H/sub 14/N/sub 8/) ] /sub 2/, III, and a novel Co(I) complex [ Co/sup I/(C/sub 10/H/sub 19/ N/sub 8/) ] , IV. Complex III is a staggered cofacial dimer with a cobalt-cobalt bond length 2.86(1).ANG.. The macrocyclic ligand of the complex contains an .alpha.- diimine function in each five-membered chelate ring, and a three-atom N-C-N/sup -/ delocalized system in each six- membered chelate ring. Complex IV has the 5-5-6-6 chelate arrangement because one .alpha.-diimine moiety is rearranged to a syn-anti configuration. In the structure, the two fused six-membered chelate rings are fully conjugated and the two fused five -membered rings are saturated. However, when complex I reacts with excess triethylamine under the similar conditions, a dimeric complex of another type, [ Co/sup II/(C/sub 10/H/sub 16/ N/sub 8/) ] /sub 2/, II, was generated, in which one N-N bond of the macrocyclic ligand is broken. Complex IV can be isolated also from the reaction of complex I with excess hydrazine, followed by slow aerial oxidation. When hydrazine in double molar proportions was used, complex [ Co/sup I/(C/sub 10/H/sub 17/N/ sub 8/)(NHNH) ] , V, which contains a coordinated diazene ligand, was obtained. Only one six-membered chelate ring of complex V is deprotonated and oxidized to form a three-atom N-C-N/sup -/ delocalized system. The structures of octa-aza complexes I- V are determined by X-ray crystallography: I, orthorhombic, C mca, a=11.646(4), b=17.049(3), c=10.706(3).ANG., Z=4, R=0.045, R/sub w/=0.047, based on 1024 reflections with I>2.sigma.(I); II, monoclinic, P2/sub 1//c, a=9.814(3), b=22.583(6), c=14.632( 9).ANG., .beta.=98.90(5).degree., Z=4, R=0.085, R/sub w/=0.101, based on 2033 reflections with I>2.sigma.(I); III, tetragonal, P4/nmm, a=15.614(3), c=6.498(2).ANG., Z=4, R=0.081, R/sub w/=0.115, based on 340 reflections with I>2.sigma.(I); IV, orthorhombic, P bca, a=8.484(1), b=16.662(3), c=18.760(2).ANG., Z=8, R=0.029, R/sub w/=0.024, based on 1441 reflections with I>2.sigma.(I); V, monoclinic, P2/sub 1//m, a=7.892(3), b=11.713(6), c=9.326(4).ANG., .beta.=108.03(3), Z=2, R=0.047, R/sub w/ =0.056, based on 948 reflections with I>2.sigma.(I).
- 英文摘要: --
- 中文關鍵字: Cobalt Complex; Macrocyclic Complex; Crystal Structure; Metal- Metal Bonding; Chemical Transformation
- 英文關鍵字: 鈷錯合物;巨環錯合物;晶體結構;金屬-金屬鍵結;化學變態