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191.
Arlen Ferrari Massimo Merlin Silvana Sostero Orazio Traverso Heinz Rüegger Luigi M. Venanzi 《Helvetica chimica acta》1998,81(11):2127-2139
Photolysis of [Ir(η2-coe)H2(TpMe2)] ( 1 ; TpMe2=hydrotris(3,5-dimethylpyrazolyl)borato, coe=(Z)-cyclooctene) in CH3OH gives a mixture of [IrH4(TpMe2)] ( 4 ) and [Ir(CO)H2(TpMe2)] ( 5 ) in a ca. 1 : 1 ratio. Mass-spectral analysis of the distillate of the reaction mixture at the end of the photolysis shows the presence of coe. When pure CD3OD is used as solvent, the deuteride complexes [IrD4(TpMe2)] ((D4)- 4 ) and [Ir(CO)D2(TpMe2)] ((D2)- 5 ) are obtained. Also the photolysis of [Ir(η4-cod)(TpMe2)] ( 3 ) (cod=cycloocta-1,5-diene) gives 4 and 5 . A key feature of this photoreaction is the intramolecular dehydrogenation of cod with formation of cycloocta-1,3,5-triene, detected by mass spectroscopy at the end of the photolysis. Labeling experiments using CD3OD show that the hydrides in 4 originate from MeOH. When 13CH3OH is used as solvent, [Ir(13CO)H2(TpMe2)] is formed demonstrating that CH3OH is the source of the CO ligand. The observation that the photolysis of both 1 and 3 give the same product mixture is attributed to the formation of a common intermediate, i.e., the coordinatively unsaturated 16e− species {IrH2(TpMe2)}. 相似文献
192.
Addition of four equivalents of t-butyldiallylphosphine 1a to a solution of one equivalent of [(COE)2IrCl]2 in CHCl3 at low temperature produced two isomers of thecomplex [t-Bu(C3H5)PCH2CH=CH)]IrHCl(COE)-[PtBu(C3H5)2] ( 2a ), which evolve at 40°C to [t-Bu(C3H5)PCH2CH=CH)]IrCl(C8H15)[PtBu(C3H5)2] ( 3a ), by a hydride transfer from iridium to the cyclooctene (COE) ligand. It is reasonable that the unsaturation at the iridium center is fulfilled by interactions with the allyl moieties of the phosphine that are not metalated. This has been demonstrated by bubbling CO into a solution of 3a in CHCl3 at room temperature to obtain the carbonyl complex [t-Bu(C3H5)-PCH2CH=CH)]Ir(CO)Cl(C8H15)[PtBu(C3H5)2] ( 4a ). Under the same conditions, the reaction of diisopropylamindiallylphosphine 1b and anisyldiallylphosphine 1c afforded a mixture of isomers 3b and 3c , respectively. These results show that diallylphosphines can be considered to be a new family of bidentate ligands. Finally, the reaction of these phosphines with [(COD)IrCl]2 (COD = 1,5 cyclooctadiene) shows the formation of tetracoordinated iridium (I) complexes IrCl(COD)(PR3), which are thermally stable. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:253–259, 1998 相似文献
193.
194.
Dr. Merlin Kleoff Patrick Voßnacker Prof. Dr. Sebastian Riedel 《Angewandte Chemie (International ed. in English)》2023,62(17):e202216586
Chlorine plays a central role for the industrial production of numerous materials with global relevance. More recently, polychlorides have been evolved from an area of academic interest to a research topic with enormous industrial potential. In this minireview, the value of trichlorides for chlorine storage and chlorination reactions are outlined. Particularly, the inexpensive ionic liquid [NEt3Me][Cl3] shows a similar and sometimes even advantageous reactivity compared to chlorine gas, while offering a superior safety profile. Used as a chlorine storage, [NEt3Me][Cl3] could help to overcome the current limitations of storing and transporting chlorine in larger quantities. Thus, trichlorides could become a key technique for the flexibilization of the chlorine production enabling an exploitation of renewable, yet fluctuating, electrical energy. As the loaded storage, [NEt3Me][Cl3], is a proven chlorination reagent, it could directly be employed for downstream processes, paving the path to a more practical and safer chlorine industry. 相似文献