The dinuclear dicationic vinylidene complex {[Ru]dCdC(Ph)CH 2 C(CH 2 CN)dCd[Ru]} 2+ (7a, [Ru] ) Cp(PEt 3 ) 2 Ru) is prepared from the reaction of ICH 2 CN with {[Ru]dCdC(Ph)CH 2 CtC[Ru]} + (6a). Deprotonation of 7a by n-Bu 4 NOH is followed by a cyclization process yielding the stable complex 9a, containing a five-membered carbocyclic ring ligand, which is fully characterized by 2D-NMR analysis and a single-crystal X-ray diffraction analysis. Similarly deprotonation of {[Ru]dCdC(Ph)CH 2 C(CH 2 -COOEt)dCd[Ru]} 2+ (8a) gave the stable product 11a containing a bridging ligand also with a similar five-membered carbocyclic ring. The cyclization process is affected by an ancillary ligand on the Ru metal center. Thus the analogous dinuclear complex 9b, with a bistriphenylphosphine ligand on one metal, which is prepared in a similar manner from] ) Cp(PPh 3 ) 2 Ru), is unstable, undergoing isomerization to give the dinuclear complex 10b, containing a cyclopropenyl ligand.
Two iron complexes each containing a 1-ferra-2,5-diphospha-[2.1.1] ring are prepared by deprotonation reaction of cationic vinylidene complexes [Fe]dCdC(Ph)CH 2 R + ([Fe] ) (η 5 -C 5 H 5 )(dppe)Fe, R ) CHd CH 2 and Ph). The deprotonation takes place at the methylene proton of the dppe ligand, which is followed by an intramolecular addition giving the product. For similar vinylidene complexes with R ) CN, p-C 6 H 4 -CN, and p-C 6 H 4 CF 3 , the deprotonation reaction gave the cyclopropenyl complexes. The deprotonation of the vinylidene complex with R ) C 6 F 5 gave both the cyclopropenyl complex and the product containing a 1-ferra-2,5-diphospha-[2.1.1] ring system. The electron-withdrawing ability of the substituent near the C γ -methylene group of the vinylidene ligand determines the selectivity of deprotonation. Characterizations of vinylidene, cyclopropenyl complexes, and a complex containing a 1-ferra-2,5-diphospha-[2.1.1] ring are carried out using single-crystal X-ray diffraction analysis.
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