TY - JOUR
T1 - The reactivity of trimethylsilyliminophosphines towards titanium and zirconium halides
AU - Sarsfield, Mark J.
AU - Said, Musa
AU - Thornton-Pett, Mark
AU - Gerrard, Lee A.
AU - Bochmann, Manfred
PY - 2001/2/22
Y1 - 2001/2/22
N2 - Zirconium tetrachloride reacted with C2H4(Ph2P=NSiMe3)2-1,2 1 under C–H activation to give the NCN chelate complex ZrCl3{?3-N,C,N'-C2H3(Ph2P=NSiMe3)2}, while the reaction with C5H3N(Ph2P=NSiMe3)2-2,6 gave an N-donor adduct. Cp*TiCl3 reacts with trimethylsilyliminophosphines under dehalosilylation in all cases. In contrast to 1, the potentially C–N chelating benzylphosphinimine (4-ButC6H4CH2)Ph2P=NSiMe3 undergoes dehalosilylation with TiCl4 in preference to C–H activation, while prolonged reflux with ZrCl4 affords the salt [4-ButC6H4CH2P(Ph)2NHSiMe3]2[Zr2Cl10]. The molecular structures of the latter, ZrCl3{C2H3(Ph2PNSiMe3)2}, C5H3N(Ph2P=NTiCl2Cp*)2-2,6, and TiCl2Cp*{N=PPh2CH2C6H4But-4} have been determined by X-ray diffraction.
AB - Zirconium tetrachloride reacted with C2H4(Ph2P=NSiMe3)2-1,2 1 under C–H activation to give the NCN chelate complex ZrCl3{?3-N,C,N'-C2H3(Ph2P=NSiMe3)2}, while the reaction with C5H3N(Ph2P=NSiMe3)2-2,6 gave an N-donor adduct. Cp*TiCl3 reacts with trimethylsilyliminophosphines under dehalosilylation in all cases. In contrast to 1, the potentially C–N chelating benzylphosphinimine (4-ButC6H4CH2)Ph2P=NSiMe3 undergoes dehalosilylation with TiCl4 in preference to C–H activation, while prolonged reflux with ZrCl4 affords the salt [4-ButC6H4CH2P(Ph)2NHSiMe3]2[Zr2Cl10]. The molecular structures of the latter, ZrCl3{C2H3(Ph2PNSiMe3)2}, C5H3N(Ph2P=NTiCl2Cp*)2-2,6, and TiCl2Cp*{N=PPh2CH2C6H4But-4} have been determined by X-ray diffraction.
U2 - 10.1039/b009082o
DO - 10.1039/b009082o
M3 - Article
SN - 1477-9234
SP - 822
EP - 827
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 6
ER -