Ruthenium Carbene, Vinylidene, and Allenylidene Complexes with a Bis(3,5-dimethylpyrazol-1-yl)acetato Heteroscorpionate Ligand

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• 作者：Henning Kopf ; Cezary Pietraszuk ; Eike H&uuml ; bner ; and Nicolai Burzlaff
• 刊名：Organometallics
• 出版年：2006
• 出版时间：May 8, 2006
• 年：2006
• 卷：25
• 期：10
• 页码：2533 - 2546
• 全文大小：575K
• 年卷期：v.25,no.10(May 8, 2006)
• ISSN：1520-6041

文摘

A series of neutral ruthenium(II) carbonyl, carbene, vinylidene, and allenylidene complexes[Ru(bdmpza)(Cl)(L)(PPh₃)] (L = C(OR')R, C=CHR, C=C=CR₂, CO) containing the bis(3,5-dimethylpyrazol-1-yl)acetato (bdmpza) ligand, an N,N,O heteroscorpionate ligand, have been prepared. Treatmentof [Ru(bdmpza)(Cl)(PPh₃)₂] (1a) with a variety of alkynes HCages/entities/tbd1.gif">CR (R = Ph, Tol, Pr, Bu) afforded thevinylidene complexes [Ru(bdmpza)(Cl)(=C=CHR)(PPh₃)] (2a-d). The carbonyl complex [Ru(bdmpza)(Cl)(CO)(PPh₃)] (3) is formed via oxidative or acid-induced degradation pathways from the vinylidenecomplexes. Reaction of 1a with the hydroxy-functionalized alkynes HCages/entities/tbd1.gif">C(CH₂)_nOH (n = 2, 3) yieldedthe cyclic Fischer type carbene complexes [Ru(bdmpza)(Cl)(=C(CH₂)₃O)(PPh₃)] (4a) and [Ru(bdmpza)(Cl)(=C(CH₂)₄O)(PPh₃)] (4b). The ruthenium(II) allenylidene complexes [Ru(bdmpza)(Cl)(=C=C=CR₂)(PPh₃)] (5a, R = Ph; 5b, R = Tol) were prepared by the reaction of 1a with propargyl alcoholsHCages/entities/tbd1.gif">CC(R)₂OH via the vinylidene intermediates [Ru(bdmpza)(Cl)(=C=CHCR₂OH)(PPh₃)]. X-ray crystalstructures of one structural isomer of the vinylidene complex [Ru(bdmpza)(Cl)(=C=CHTol)(PPh₃)](2b), the carbonyl complex [Ru(bdmpza)(Cl)(CO)(PPh₃)] (3), the carbene complex [Ru(bdmpza)(Cl)(=C(CH₂)₄O)(PPh₃)] (4b-I), and two structural isomers of [Ru(bdmpza)(Cl)(=C=C=CPh₂)(PPh₃)] (5a-Iand 5a-II) are reported.