手性金属钼配合物：光学活性合成与分子结构

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"这篇学术论文详细探讨了光学活性过渡金属复合物，特别是关于手性金属环庚三烯基-亚氨基膦-钼复合物的研究。作者包括Henri Brunner、Jürgen Klankermayer和Manfred Zabel，来自德国雷根斯堡大学无机化学研究所。该研究于2002年2月27日提交，并献给Dieter Fenske教授以庆祝他的60岁生日。论文主要关注两个仅在钼配置上有所不同的手性钼化合物：(RMo,SC)-[(η7-C7H7)Mo(iminphos)(CO)]BF4(2a)和(SMo,SC)-[(η7-C7H7)Mo(iminphos)(CO)]BF4(2b)，其中iminphos是2-[N-(S)-1-苯基乙基羰亚胺]苯基（二苯基）膦烷。这两种复合物通过分级结晶方法成功合成并分离。绝对构型的确定是通过实验方法完成的，这在理解这些复杂分子的光学性质和反应性方面至关重要。手性过渡金属复合物在催化、不对称合成和材料科学等领域具有广泛的应用。这些特定的钼复合物由于其独特的金属配位结构，可能展示出独特的光学性质，如旋光性和圆二色性，这使得它们成为研究手性催化剂设计和手性识别机制的理想模型。此外，通过对这些化合物的分子结构进行深入分析，可以揭示金属配位环境对手性控制的影响，这对于优化化学反应的立体选择性具有重要意义。论文的实验部分可能包括化合物的合成步骤、结构鉴定技术（如X射线晶体学、红外光谱、核磁共振等）、以及光学性质的测定。分子结构的比较将揭示金属配位构型变化如何影响整个分子的立体构象，从而影响其光学性质。这些研究成果对于理解和开发新的高效手性催化剂，特别是在药物合成和精细化学品制造中，都具有重要的理论和实际价值。这篇论文为光学活性过渡金属复合物的合成、表征和分子结构研究提供了新的见解，特别是关注那些仅在金属配置上差异的钼复合物，这为手性化学领域提供了宝贵的贡献。"

Optically Active Transition Metal Complexes. 128 [1]

Synthesis, Characterization and Molecular Structures of Cycloheptatrienyl-

Iminphos-Molybdenum Complexes Differing Only in the Metal Configuration

Henri Brunner*, Jürgen Klankermayer, and Manfred Zabel

Institut für Anorganische Chemie, Universität Regensburg

Received February 27th, 2002.

Dedicated to Professor Dieter Fenske on the Occasion of his 60th Birthday

Abstract. The chiral-at-metal cycloheptatrienyl-molybdenum

complexes (R

)-[(η

-C

)Mo(iminphos)(CO)]BF

(2a) and

)-[(η

-C

)Mo(iminphos)(CO)]BF

(2b) (iminphos ⫽ 2-[N-

(S)-1-phenylethylcarbaldimino]phenyl(diphenyl)phosphane), which

only differ in the molybdenum configuration, were prepared and

separated by fractional crystallization. The absolute configuration

Optisch aktive Übergangsmetall-Komplexe. 128 [1]

Synthese, Charakterisierung und Molekülstrukturen von chiralen Cycloheptatrienyl-

Iminphos-Molybdän-Komplexen mit unterschiedlicher Metallkonfiguration

Inhaltsübersicht. Die am Metall chiralen Cycloheptatrienyl-Molyb-

dän-Komplexe (R

)-[(η

-C

)Mo(iminphos)(CO)]BF

(2a)

und (S

)-[(η

-C

)Mo(iminphos)(CO)]BF

(2b) (iminphos ⫽

2-[N-(S)-1-Phenylethylcarbaldimino]phenyl(diphenyl)phosphan),

die sich nur in der Konfiguration am Molybdänatom unterschei-

Introduction

Three-legged “piano stool” complexes of the type [(η

)MLL⬘L⬙] are well known examples of chiral-at-metal

compounds [2, 3, 4]. Provided, one of the ligands, e.g. an

unsymmetrical chelate ligand L⫺L⬘, is enantiomerically

pure, a pair of diastereomers arises, differing only in the

metal configuration. Usually, such diastereomers can be

distinguished on the basis of their NMR spectra. Then, the

diastereomer ratio can be determined by the integration of

suitable signals.

Generally, the diastereomer, which is the less soluble or

present in excess, can be separated from a diastereomer

mixture on crystallization [2, 3, 4]. This is the basis of dia-

stereomer separation by fractional crystallization. Interest-

ingly, for configurationally labile compounds, frequently en-

countered among half-sandwich complexes, asymmetric

* Prof. Dr. Henri Brunner

Institut für Anorganische Chemie, Universität Regensburg

D-93040 Regensburg, Germany

Fax: (internat.) ⫹49-(0)941/943-4439

E-mail: henri.brunner@chemie.uni-regensburg.de

X-ray structure analyses

2264  WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044⫺2313/02/628/2264⫺2268 $ 20.00⫹.50/0 Z. Anorg. Allg. Chem. 2002, 628, 2264⫺2268

for both diastereomers was determined by X-ray analysis.

H NMR

studies demonstrated the configurational lability at the molyb-

denum centre in solution.

Keywords: Chirality; Molybdenum; Half-sandwich complexes; Me-

tal configuration

den, wurden dargestellt und durch fraktionierende Kristallisation

getrennt. Die absolute Konfiguration wurde für beide Diastereo-

mere durch Kristallstrukturanalyse bestimmt. Durch

H-NMR-

spektroskopische Untersuchungen konnte die Konfigurationslabili-

tät des Metallzentrums nachgewiesen werden.

transformations may be involved [4, 5]. To the best of our

knowledge, there are so far only two examples of chiral-at-

metal compounds, for which the molecular structures of

both diastereomers could be determined by X-ray crystal-

lography [6, 7]. In the present paper we describe another

example: the synthesis, separation and characterization of

diastereomeric cycloheptatrienyl-molybdenum half-sand-

wich complexes of the type [(η

-C

)Mo(iminphos)-

(CO)]BF

and the determination of the molecular structures

of both diastereomers [8].

Results and Discussion

Synthesis of the compounds 1 and 2

Treatment of the reactive complex [(η

-C

)Mo(η

)]BF

[9] with the chiral phosphaneimine 2-[N-

(S)-1-phenylethylcarbaldimino]phenyl(diphenyl)phosphane,

(S)-iminphos [10, 11], in CH

CN resulted in the formation

of a diastereomer mixture of [(η

-C

)Mo(imin-

phos)(NCMe)]BF

(1) (Scheme 1). The diastereomer ratio

could be determined by

H NMR spectroscopy as 55:45

in [D

]acetone.

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