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Yuchun Jiang Xia Zhu Yu Wang Francis Verpoort Xiaohong Chang 《Inorganica chimica acta》2011,376(1):144-151
μ-Chloro bridged dinuclear cyclometallated Pd(II) complexes [Pd{(4-R)C6H3CHNC6H3-2,6-i-Pr2}(μ-Cl)]2 (R = H, OMe) were prepared by reaction of Na2PdCl4 with benzylideneanilines. Unexpectedly, Na2PdCl4 reacted with Schiff-bases bearing a furyl or a thienyl ring to give N-coordinated non-cyclometallated Pd(II) species [Pd(C4H3XCHNC6H3-2,6-i-Pr2)2Cl2] (X = O, S). Treating [Pd{(4-R)C6H3CHNC6H3-2,6-i-Pr2}(μ-Cl)]2 (R = H, OMe) with an excess of NaN3 or NH4SCN generated μ-N3 bridged or μ-SCN bridged cyclometallated Pd(II) complexes [Pd{(4-R)C6H3CHNC6H3-2,6-i-Pr2}(μ-Y)]2 (R = H, OMe; Y = N3, NCS). The complexes were characterized by FTIR, NMR spectroscopy, elemental analysis and X-ray crystallography. 相似文献
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Rodolphe F.R. Jazzar Andrew D. Burrows Stuart A. Macgregor Mary F. Mahon 《Inorganica chimica acta》2006,359(3):815-820
Two isomers of the N,O-coordinated acetylpyrrolyl complex [Ru(PPh3)2(CO)(NC4H3C(O)CH3)H] {cis-N,H (1) and trans-N,H (2)} have been prepared as models for catalytic intermediates in the Murai reaction. Complex 2 isomerises to 1 upon heating via a dissociative pathway (ΔH‡ = 195 ± 41 kJ mol−1; ΔS‡ = 232 ± 62 J mol−1 K−1); the mechanism of this process has been modeled using density functional calculations. Complex 2 displays moderate catalytic activity for the Murai coupling of 2′-methylacetophenone with trimethylvinylsilane, but 1 proved to be catalytically inactive under the same conditions. 相似文献
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Carola S. Vogel 《Inorganica chimica acta》2010,364(1):226-237
The chelating ligand tris-[2-(3-aryl-imidazol-2-ylidene)ethyl]amine (TIMENR, R = aryl = 2,6-xylyl (xyl), mesityl (mes)) has provided access to reactive transition metal complexes. Here, two new tripodal N-heterocyclic carbene ligands of the TIMENR system (R = aryl = tolyl (tol), 3,5-xylyl (3,5xyl)), featuring sterically less demanding aryl substituents were synthesized. With these ligands, Fe(II) precursor complexes could be obtained, namely [(TIMENtol)Fe](BF4)2 (3) and [(TIMEN3,5xyl)Fe(CH3CN)](PF6)2 (7), which showed unexpected reactivity upon reduction. Treatment of the compounds with sodium amalgam yield the tris- and bis-metallated products, [(TIMENtol∗∗∗)Fe] (4) and [(TIMEN3,5xyl∗∗)Fe] (8), respectively. While the Fe(III) complex 4 is relatively inert towards oxygen, the Fe(II) complex 8 is prone to oxidation. This oxidation of 8 can readily be observed in chlorinated solvents, producing the Fe(III) complex [(TIMEN3,5xyl∗∗)Fe](PF6) (9). All new ligand imidazolium precursors and metal complexes were characterized by single crystal X-ray structure determination. 相似文献
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Jahar Lal Pratihar Debprasad Patra Surajit Chattopadhyay 《Inorganica chimica acta》2011,367(1):182-186
Reactions of 2-(arylazo)aniline, HL (H represents the dissociable protons upon orthometallation and HL is p-RC6H4NNC6H4-NH2; RH for HL1; CH3 for HL2 and Cl for HL3) with IrCl3 in methanol afforded orthometallated complexes of composition (L)(HL)IrCl2 (2) and (L)(MeOH)IrCl2 (3), respectively. Complex (L)(MeOH)IrCl2 (3) converted into (L)(CH3CN)IrCl2 (4) upon refluxing in acetonitrile. The X-ray structure of the complexes (L1)(HL1)IrCl2 (2a) and (L3)(CH3CN)IrCl2 (4c) have been determined and characterized unequivocally. The anionic L− binds the metal in tridentate (C, N, N) manner for all the complexes. 相似文献
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Michel Pfeffer Jean-Pascal SutterAndr DeCian Jean Fischer 《Inorganica chimica acta》1994,220(1-2):115-127
The Pd---C bond of the cyclopalladated derivative of dimethylaminomethylferrocene (1) is fairly reactive to insertion of conjugated dienes such as 1,3-butadiene, isoprene, 2,3-dimethylbutadiene or 1,3-cyclohexadiene. This reaction affords organopalladium complexes containing an η3-allyl-Pd moiety where the NMe2 unit of the starting material is still intramolecularly coordinated to Pd. These complexes are stable in solution but in MeOH in the presence of PPh3, reductive elimination of Pd is observed. This occurs whilst a nucleophilic intramolecular addition of the NMe2 group to the allylic fragment takes place, affording six-, seven- or eight-membered heterocyclic compounds. The importance of the steric effects of the substituents on the butenyl chain upon the course of the reaction has been investigated. 相似文献
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Reaction of 2 equivalents of 1,3-bis-(di-tert-butylphosphinito)-2-methyl-propane (1a) with [Ir(COD)Cl]2 affords the first aliphatic diphosphinite PCP pincer complex with iridium, Ir(H){(t-Bu2POCH2)2C(Me)}Cl (2). The poor yield of 2 is partly explained by the formation of a di-nuclear byproduct [IrCl(COD)]2(μ2-{(t-Bu2POCH2)2CH(Me)}) (3). Reaction of 1,3-bis-(di-iso-propylphosphinito)-2-methyl-propane (1b) under the same condition does not give any cyclometallation, and reaction with IrCl3·H2O in DMF leads to complete decomposition of the pincer ligand under the formation of Ir(H)(i-Pr2P(OH))3(CO) (4), underpinning the comparatively low thermal stability of aliphatic phosphinite pincer systems. 相似文献
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