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Title of article :
Mono- and bis-[2-(P,P-dimethylphosphanyl)ethyl]tetramethylcyclopentadienyl zirconium(IV) complexes: Synthesis and structural studies in crystalline state and in solutions
Author/Authors :
Dmitrii P. Krut’ko، نويسنده , , Maxim V. Borzov، نويسنده , , Edward N. Veksler، نويسنده , , Andrei V. Churakov، نويسنده , , Lyudmila G. Kuz’mina، نويسنده ,
Issue Information :
دوفصلنامه با شماره پیاپی سال 2005
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Abstract :
Synthetic routines for a new ligand C5Me4CH2CH2PMe2 (2b) in forms of its Li- (2b-Li), Na- (2b-Na) salts and in the CH-form (2b-H), as well as for silanes Me3Si-C5H4CH2CH2PMe2 (3a) and Me3Si-C5Me4CH2CH2PMe2 (3b) have been developed. On the basis of it, new half-sandwich [η5:η1-κP-C5H4CH2CH2PMe2]ZrCl3 (4a), [η5:η1-κP-C5Me4CH2CH2PMe2]ZrCl3 (4b) and sandwich [η5-C5Me4CH2CH2PMe2]2ZrCl2 (5), [η5-C5Me4CH2CH2PMe2][η5-C5Me5]ZrCl3 (6) complexes of Zr(IV) have been prepared and characterized. Along with them, the first example of X-ray structurally characterized dinuclear Zr(IV) complex incorporating both sandwich (6) and half-sandwich (4b) moieties linked one to another by means of Zr ← P coordination bond 7, has been described. Formation of an analogously organized trinuclear complex 8, built from one sandwich fragment of 5 and two half-sandwich fragments of 4b was proved by NMR spectroscopy methods. Molecular structures of half-sandwich complexes in their solvent-free dimeric forms (4a and 4b) and as 1:1 adducts with THF (4a-THF and 4b-THF) along with those of dinuclear complex 7 have been established by X-ray diffraction analyses. The dynamic behavior for di- and trinuclear complexes 7 and 8, due to the intermolecular dissociation–coordination of the Me2P-groups in THF-d8 solutions has been studied by variable-temperature NMR spectroscopy.
Keywords :
Cyclopentadienyl ligands , Dynamic behavior , Intramolecular coordination , P ligands , Zirconium
Journal title :
Journal of Organometallic Chemistry
Journal title :
Journal of Organometallic Chemistry
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