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Synthesis and Structure of New Dimeric Cyclopentadienyl Titanium Fluorine–Oxygen Systems: [Cp*TiF(μ‐F)(μ‐OPOPh 2 )] 2 , [Cp*TiF(μ‐F)(μ‐OSO 2 ‐ p ‐C 6 H 4 Me)] 2 and [Cp*TiF 2 (μ‐OMe)] 2
Author(s) -
Gindl Judith,
Said Musa A.,
Yu Peihua,
Roesky Herbert W.,
Noltemeyer Mathias,
Schmidt HansGeorg
Publication year - 1999
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.199900014
Subject(s) - chemistry , monoclinic crystal system , crystallography , cyclopentadienyl complex , denticity , fluorine , crystal structure , oxygen atom , ligand (biochemistry) , tetramer , nmr spectra database , stereochemistry , spectral line , molecule , biochemistry , enzyme , receptor , physics , organic chemistry , astronomy , catalysis
Abstract The reactions of Cp*TiF 3 with Me 3 SiOPOPh 2 , Me 3 SiOSO 2 ‐ p ‐C 6 H 4 Me, and Al(OMe) 3 resulted in the formation of the dimers [Cp*TiF(μ‐F)(μ‐OPOPh 2 )] 2 1 , [Cp*TiF(μ‐F)(μ‐OSO 2 ‐ p ‐C 6 H 4 Me)] 2 2 , and [Cp*TiF 2 (μ‐OMe)] 2 3 , respectively, in good yields. In contrast to the formation of 3 , Cp*TiF 3 reacts with Al(OH) 3 to afford the known tetramer [Cp*TiF(μ‐O)] 4 4 . The structures of 1–3 have been determined by X‐ray crystallography; compounds 1 and 3 crystallize in the monoclinic space group P 2 1 /c and compound 2 in the monoclinic space group P 2 /n . Compound 1 is the first example of a dimeric Cp*‐titanium phosphinate containing a fluorine ligand. The core of the dimeric structure of both 1 and 2 consists of two Ti atoms bridged by two fluorine atoms and two bidentate groups. In contrast, the dimeric structure of 3 consists of two Ti atoms bridged only by two methoxy groups. An equilibrium of isomers of 1 and 2 has been observed in solution by 1 H and 19 F NMR. The 19 F NMR spectra of 1–3 are discussed in detail.