1088680-99-2Relevant academic research and scientific papers
Synthesis, structures and reactivity of group 4 hydrazido complexes supported by calix[4]arene ligands
Clulow, Andrew J.,Selby, Jonathan D.,Cushion, Michael G.,Schwarz, Andrew D.,Mountford, Philip
, p. 12049 - 12062 (2009/06/05)
Reaction of TiCl2(Me2Calix) with 2 equiv of LiNHNRR′ afforded the corresponding terminal hydrazido(2-) complexes Ti(NNRR′)(Me2Calix) (R = Ph, R′ = Ph (1) or Me; R = R′ = Me (3)) which were all structurally characterized. The X-ray structure of Ph2NNH2 is reported for comparison. Compound 1 was also prepared from Na2[Me2Calix] and Ti(NNPh 2)Cl2(py)3. Reaction of ZrCl 2(Me2Calix) with 2 equiv of LiNHNR2 afforded only the bis(hydrazido(1-)) complexes Zr(NHNR2)2(Me 2Calix) (R = Ph or Me). Treatment of Ti(NNMe2)(Me 2Calix) (3) with Mel gave the zwitterionic hydrazidium species Ti(NNMe3)(MeCalix) (6) via a net isomerization reaction which was found to be catalytic in Mel. The corresponding reaction of 3 with CD 3I gave Ti(NNMe2CD3)(MeCalix) (6-d3) with concomitant elimination of Mel. Reaction of 3 with 1 equiv of MeOTf gave [Ti(NNMe3)(Me2Calix)][OTf] (7-OTf) which in turn reacted with nBu4NI to form 6 and Mel. Addition of PhCHO to 3 gave the μ-oxo dimer [Ti(μ-O)(Me2Calix)]2 and benzaldehydedimethylhydrazone. Reaction of either 3 or 6 with tBuNCO gave the zwitterionic species Ti{tBuNC(NNMe3)O}(MeCalix) (10) which has been crystallographically characterized. Compound 10 is the formal product of insertion of an isocyanate into the Ti=Nα. bond of a titanium hydrazide or hydrazidium species (Me2Calix or MeCalix = dianion or trianion of the di- or monomethyl ether of p-tert-butyl calix[4]arene, respectively).
