通过不对称铁氢化酶活性位点模拟物的质子化形成末端氢化物的证据。
Evidence for the formation of terminal hydrides by protonation of an asymmetric iron hydrogenase active site mimic.
作者信息
Ezzaher Salah, Capon Jean-François, Gloaguen Frédéric, Pétillon François Y, Schollhammer Philippe, Talarmin Jean, Pichon Roger, Kervarec Nelly
机构信息
Chimie, Electrochimie Moléculaires et Chimie Analytique, Faculté des Sciences, UMR CNRS 6521, Université de Bretagne Occidentale, 6 Avenue Le Gorgeu, CS 93837, 29238 Brest Cedex 3, France.
出版信息
Inorg Chem. 2007 Apr 30;46(9):3426-8. doi: 10.1021/ic0703124. Epub 2007 Mar 31.
Treatment of [Fe2(mu-pdt)(CO)6] [pdt=S(CH2)3S] with dppe (Ph2PCH2CH2PPh2) in refluxing toluene affords the asymmetric complex [Fe2(mu-pdt)(CO)4(dppe)] (1). Protonation of 1 with HBF4-Et2O in CH2Cl2 gives at room temperature the mu-hydrido derivative Fe2(mu-pdt)(CO)4(dppe)(mu-H) (2). Monitoring the reaction by 1H, 31P, and 13C NMR at low temperature reveals unambiguously that the process of the protonation of 1 implies terminal hydride intermediates.
在回流的甲苯中，用双（二苯基膦）乙烷（dppe，Ph2PCH2CH2PPh2）处理[Fe2(μ-pdt)(CO)6] [pdt = S(CH2)3S]，得到不对称配合物[Fe2(μ-pdt)(CO)4(dppe)]（1）。在二氯甲烷中，1与HBF4-Et2O在室温下发生质子化反应，生成μ-氢化物衍生物Fe2(μ-pdt)(CO)4(dppe)(μ-H)（2）。在低温下通过1H、31P和13C核磁共振监测反应，明确显示1的质子化过程涉及末端氢化物中间体。
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