Selective Tin−Carbon Bond Cleavage Reactions of Trimethylstannylzirconocene Dichloride with Electrophiles

The reaction of 5,5-bis(trimethylstannyl)cyclopentadiene with CpZrCl3 (Cp = η5−C5H5) affords the monostannylated metallocene complex (η5−Me3SnC5H4)CpZrCl2 (1), accompanied by variable amounts of (η5−ClMe2SnC5H4)CpZrCl2 (2). The complex (1) reacts with BCl3 or with ICl to afford 2 (Sn−CH3 cleavage), but with
HCl, Cp2ZrCl2 is obtained instead (Sn−Cp cleavage). Depending on the reaction conditions, treatment of either
1 or 2 with BBr3 affords (η5−BrMe2SnC5H4)CpZrBr2 (3) or (η5−Br2MeSnC5H4)CpZrBr2 (4). The reaction of 1
with excess I2 affords the iodostannylated complex (η5−IMe2SnC5H4)CpZrCl2 (5). Two of the complexes (2·2C6H5CH3 and 4·THF) are crystallographically characterized. The adduct 4·THF has a distorted trigonal
bipyramidal geometry about tin with a long O−Sn distance of 2.655 Å. We find overall that Me3Sn substituents
undergo electrophilic halodemethylation much more readily than corresponding Me3Si substituents, whereas the
reactivities of the halostannylated complexes toward nucleophiles such as airborne moisture are much lower than
those of their halosilylated counterparts.