Direct crystallographic observation of a coordinatively unsaturated transition-metal complex in situ generated within a self-assembled cage

Masaki Kawano; Yasuhiro Kobayashi; Tomoji Ozeki; Makoto Fujita

doi:10.1021/ja0609250

Direct crystallographic observation of a coordinatively unsaturated transition-metal complex in situ generated within a self-assembled cage

J Am Chem Soc. 2006 May 24;128(20):6558-9. doi: 10.1021/ja0609250.

Authors

Masaki Kawano¹, Yasuhiro Kobayashi, Tomoji Ozeki, Makoto Fujita

Affiliation

¹ Department of Applied Chemistry, School of Engineering, The University of Tokyo, Japan. mkawano@appchem.t.u-tokyo.ac.jp

PMID: 16704246
DOI: 10.1021/ja0609250

Abstract

In situ crystallographic observation of an extremely labile coordinatively unsaturated transition-metal complex, Cp'Mn(CO)2 (Cp' = methylcyclopentadienyl), was achieved by generating and trapping it within the confined cavity of a self-assembled cage in the crystalline state at a low temperature. The labile target Cp'Mn(CO)2 was formed by the photodissociation of the CO ligand from stable Cp'Mn(CO)3, which was accommodated within the cavity of the coordination cage. Being trapped in the cage at a low temperature, Cp'Mn(CO)2 showed sufficient stability to be analyzed by X-ray crystallography. The diffraction study revealed that the 16-electron unsaturated Mn complex adopted a pyramidal geometry rather than a planar geometry.