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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Synthesis and Protonation Studies of Molybdenum(0) Bis(dinitrogen) Complexes Supported by Diphosphine Ligands Containing Pendant Amines
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Synthesis and Protonation Studies of Molybdenum(0) Bis(dinitrogen) Complexes Supported by Diphosphine Ligands Containing Pendant Amines

机译:含侧链胺的二膦配体负载的钼(0)双(二氮)配合物的合成和质子化研究

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摘要

A series of molybdenum bis(dinitrogen) complexes of the formula trans-[Mo(N-2)(2)((PNPEt)-N-Et-P-R)(2)] ((PNPEt)-N-Et-P-R = Et2PCH2N(R)CH2PEt2; R = phenyl (1), 2,6-difluorobenzyl (2), 3,5-difluorobenzyl (3), CH2CH2NMe2 (4), CH2-o-Py (5)] were synthesized and characterized by NMR and IR spectroscopy, and X-ray crystallography. Protonation studies with stoichiometric amounts of triflic acid (HOTf) were performed, and the protonated products were characterized by NMR and in situ IR spectroscopic methods. Products formed in the stepwise protonation reactions included, for example, a mixture of the seven-coordinate molybdenum bis(dinitrogen) hydride, trans-[Mo(H)(N-2)(2)((PNPEt)-N-Et-P-Ph)(2)](+) [H-1](+), and the Mo-hydrazido triflate complex, trans-[Mo(NNH2)(OTf)((PNPEt)-N-Et-P-Ph)(2)](+) [(1)(NNH2)](+). Complex 2, with more basic pendant amines, can be protonated up to three times, affording the highly-charged molecule, trans[Mo(H)(N-2)(2)((PN2,6-F2-Bn)-N-Et(H)P-Et)(2))](3+) [2H(PN(H)P)(2)](3+).
机译:分子式为反式-[Mo(N-2)(2)((PNPEt)-N-Et-PR)(2)]的一系列钼双(二氮)配合物((PNPEt)-N-Et-PR = Et2PCH2N(R)CH2PEt2;合成R =苯基(1),2,6-二氟苄基(2),3,5-二氟苄基(3),CH2CH2NMe2(4),CH2-o-Py(5)] NMR,IR光谱和X射线晶体学:用化学计量的三氟甲磺酸(HOTf)进行质子化研究,并通过NMR和原位红外光谱法对质子化产物进行表征,包括在逐步质子化反应中形成的产物,用于例如,七配位的双(二氮)氢化钼钼,反式-[Mo(H)(N-2)(2)((PNPEt)-N-Et-P-Ph)(2)] [+ )[H-1](+)和Mo-肼基三氟甲磺酸盐络合物,反式-[Mo(NNH2)(OTf)((PNPEt)-N-Et-P-Ph)(2)](+)[( 1)(NNH2)](+)。具有更多碱性侧基胺的配合物2可以质子化多达3次,从而提供高电荷分子trans [Mo(H)(N-2)(2)(( PN2,6-F2-Bn)-N-Et(H)P-Et)(2))](3+)[2H(PN(H)P)( 2)](3+)。

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