Abstract
Titanocene complexes [Ti(η(5)-C5H5-nMen)(2)(η(2)-Me3SiC=CSiMe3)] (n = 0, 4 and 5) react uniformly with siladiynes (R2SI)-S-2(C=CR1)(2),, where R-1 = Ph, and R-2 = Ph or Me, at elevated temperature in hydrocarbon solvents to give the corresponding silacyclobutene-annelated titanacyclobutene complexes, 3-bis(η(5)-cyclopentadienyl)titana-6-diorganylsilabicyclo[2.2.0]hexa-1(2),4(5)-dienes, [(η(5)-C5H5-nMen)(2)Ti{(R2C4)-C-1(SiR22)}]. Products arising from [Ti(η(5)-C5H5-nMen)(2)(η(2)-Me3SiC=CSiMe3)] (n = 0, 2 (1,3-isomer), 4 and 5) and Me2Si(C=CCMe3)(2) vary with n: the non-methylated titanocene complex affords a mixture of an analogous silacyclobutene-annelated titanacyclobutene and [{Ti(η(5)-C5H5)(2)}(2){μ-η(3-5):η(4-6)-Me3CC=CC=CCMe3}], the permethylated titanocene precursor gives mainly the allyldiene complex [Ti(η(5)-C5Me5)(η(3):η(4)-C5Me3(CH2)(2))] while no titanium-containing product could be isolated for n = 4.
The reaction of [Ti(η(5)-1,3-C5H3Me2)(2)(η(2)-Me3SiC=CSiMe3)] with Me2Si(C=CCMe3)(2), however, cleanly affords the expected silacyclobutene-titanacyclobutene complex. All complexes were studied by spectral methods and solid-state structure of two representatives, [(η(5)-C5Me5)(2)Ti{Ph2C4(SiMe2)}] and [(η(5)-1,3-C5H3Me2)(2)Ti{(Me3C)(2)C-4(SiMe2)}] was determined by single-crystal X-ray diffraction.