Abstract
The mono(guanidinato) complex Cp(guan)ZrCl2 (1; guan = η2-(iPrN)2C(NMe2)) was prepared by treatment of CpZrCl3 (Cp = η5-C5H5) with the in situ generated lithium guanidinate salt 2. The dimethylamino group of 1 resists quaternization by alkylating and silylating reagents. Complex 1 undergoes ligand redistribution when treated with 2 equiv of MeLi, but reaction with 2 equiv of MeMgCl affords the dimethyl derivative Cp(guan)ZrMe2 (3). Insertion of 2 equiv of diisopropylcarbodiimide into the Zr−N bonds of (Me2N)2ZrCl2(THF)2 produces the bis(guanidinato)zirconium dichloride complex (guan)2ZrCl2 (4). Alkylation of 4 with 2 equiv of MeLi or PhCH2MgCl affords the dialkyl derivatives (guan)2ZrMe2 (5) and (guan)2Zr(CH2Ph)2 (6), respectively. Variable-temperature NMR experiments on 6 reveal a limiting C2-symmetric solution structure at 253 K. Complex 5 undergoes reaction with electrophiles (Me3SiOTf (OTf = OSO2CF3), B(C6F5)3, [Ph3C][B(C6F5)4]) to yield stable products of methide abstraction: neutral complexes (guan...
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