1,1'-BIS(N,N-DIMETHYLAMINO)FERROCENE, 1,1'-BIS(N,N-DIMETHYLAMINO)COBALTOCENIUM HEXAFLUOROPHOSPHATE AND 1,1'-BIS(N,N-DIMETHYLAMINO)TITANOCENE DICHLORIDE. CRYSTAL STRUCTURE OF 1,1'-BIS(N,N-DIMETHYLAMINO)TITANOCENE DICHLORIDE

Article abstract of DOI:10.1016/0022-328X(84)80686-5

A general method for the preparation of 1,1'-bis(N,N-dimethylamino)metallocenes is described, involving the reaction of N,N-dimethylamino-cyclopentadienyllithium (1-Li) with metal chlorides. 1,1'-Bis(N,N-dimethylamino)ferrocene (2), 1,1'-bis(N,N-dimethylamino)cobaltocenium hexafluorophosphate (3⁺ PF6^-) and 1,1'-bis(N,N-dimethylamino)titanocene dichloride (4) have been synthesized in this way.The influence of the dimethylamino donor substituent has been studied by means of cyclic voltammetry. 1,1'-Bis(N,N-dimethylamino)ferrocene (2), e.g., has the most negativeredox potential (E^o -0.23 V (SCE)) so far reported for a ferrocene derivative.The structure of 1,1-bis(N,N-dimethylamino)titanocene dichloride (4) has been determined by X-ray crystallography.It crystallizes in hexagonal plates with the space group C2/c (Z = 4, a 1301.4, b 647.2, c 1828.5 pm, β 98.81 deg).The titanium atom does not lie exactly above the centers of the cyclopentadienyl rings, and the C-N bond from the cyclopentadienyl ring carbon atom C(1) to the nitrogen atom of the dimethylamino group is very short (134.7 pm).