Preparation, facile deprotonation, and rapid H/D exchange of the mu-hydride diiron model complexes of the [FeFe]-hydrogenase containing a pendant amine in a chelating diphosphine ligand.-猫眼课题宝

DOI：

10.1021/ic901154m

发表时间：

2009-11

期刊：

Inorganic chemistry

影响因子：

4.6

通讯作者：

中科院分区：

化学2区

文献类型：

作者：

Ning Wang;Mei Wang;Jihong Liu;Kun Jin;Lin Chen;Licheng Sun

[（mu-pdt）Fe（2）（CO）（6）]与（Ph（2）PCH（2））（2）N（n-Pr）在正甲苯中进行CO置换反应，得到不对称螯合物[（mu-pdt）{Fe（CO）（3）}{Fe（CO）（kappa（2）-Ph（2）PCH（2）N（n-Pr）CH（2）PPh（2）}]（1），与少量对称的分子内桥连络合物[（mu-pdt）{mu-Ph（2）PCH（2）N（n-Pr）CH（2）PPh（2）}{Fe（CO）（2）}（2）]（2）和分子间桥连络合物[{mu，kappa（1），kappa（1）-Ph（2）PCH（2）N（n-Pr）CH（2）PPh（2）}{（mu-pdt）Fe（2）（CO）（5）}（2）]（3）。与此相反，[（mu-pdt）Fe（2）（CO）（6）]与（Ph（2）PCH（2））（2）NR（R = n-Pr，Ph）在脱CO试剂Me（3）NO.2H（2）O存在下于CH（3）CN中于室温下反应得到分子间桥连异构体3和4。通过X射线衍射分析确定了1、3和4以及双质子化配合物[1（H（N）H（mu））]（OTf）（2）]的分子结构。研究了1与HBF（4）、Et（2）O和HOTf在不同溶剂中的质子化反应。H（mu）的存在...用弛豫时间T（1）和自旋饱和转移测量研究了[1（H（N）H（mu））]（2+）中H（N）相互作用. [1（H（mu））]（+）和[1（H（N）H（mu））]（2+）的μ-氢化物在溶液中与苯胺发生容易的去质子化和与氘的快速H/D交换。与此相反，没有内部碱的[（mu-H）（mu-pdt）{Fe（CO）（3）}{Fe（CO）（kappa（2）-dppp）}]（+）（[5（H（mu））]（+），dppp = Ph（2）PCH（2）CH（2）CH（2）PPh（2））既没有检测到去质子化也没有检测到H/D交换。

The CO-displacement of [(mu-pdt)Fe(2)(CO)(6)] with (Ph(2)PCH(2))(2)N(n-Pr) in refluxing toluene gave an unsymmetrical chelating complex [(mu-pdt){Fe(CO)(3)}{Fe(CO)(kappa(2)-Ph(2)PCH(2)N(n-Pr)CH(2)PPh(2)}] (1) as a major product, together with a small amount of the symmetrical intramolecular bridging complex [(mu-pdt){mu-Ph(2)PCH(2)N(n-Pr)CH(2)PPh(2)}{Fe(CO)(2)}(2)] (2) and the intermolecular bridging complex [{mu,kappa(1),kappa(1)-Ph(2)PCH(2)N(n-Pr)CH(2)PPh(2)}{(mu-pdt)Fe(2)(CO)(5)}(2)] (3). In contrast, the reaction of [(mu-pdt)Fe(2)(CO)(6)] with (Ph(2)PCH(2))(2)NR (R = n-Pr, Ph) afforded the intermolecular bridging isomers 3 and 4 in the presence of a CO-removing reagent Me(3)NO.2H(2)O in CH(3)CN at room temperature. The molecular structures of 1, 3, and 4, as well as the doubly protonated complex [1(H(N)H(mu))](OTf)(2)] were determined by X-ray analyses. The protonation processes of 1 with HBF(4).Et(2)O and HOTf were studied in different solvents. The presence of the H(mu)...H(N) interaction in [1(H(N)H(mu))](2+) was studied by relaxation time T(1) and spin saturation transfer measurements. The mu-hydride of [1(H(mu))](+) and [1(H(N)H(mu))](2+) undergo facile deprotonation with aniline and rapid H/D exchange with deuterons in solution. In contrast, neither deprotonation nor H/D exchange was detected for [(mu-H)(mu-pdt){Fe(CO)(3)}{Fe(CO)(kappa(2)-dppp)}](+) ([5(H(mu))](+), dppp = Ph(2)PCH(2)CH(2)CH(2)PPh(2)) without internal base.

Preparation, facile deprotonation, and rapid H/D exchange of the mu-hydride diiron model complexes of the [FeFe]-hydrogenase containing a pendant amine in a chelating diphosphine ligand.

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