有机锡修饰的双吡唑甲烷及其与W(CO)5THF的反应

通过双吡唑甲基锂(LiCHPz2)与有机锡卤化物(R3SnX)的反应合成了一系列有机锡修饰的双吡唑甲烷配体(R3SnCHPz2),由于锡上取代基的不同，这些配体与W(CO)5THF反应时表现出了不同的反应方式，三芳基锡修饰的双吡唑甲烷与W(CO)5THF反应发生Sn-C(sp^3)键对W(0)中心的氧化加成;而三苄基锡修饰的双吡唑甲烷与其反应时仅给出羰基取代产物Bz3SnCHPz2W(CO)4]，另外，二苯基苄基锡以及三(2-苯基-2-甲基丙基)锡修饰的双吡唑甲烷配体类似的反应导致配体的分解，产生单吡唑配体取代的羰基钨衍生物W(CO)5PzH]以及脱有机锡的双吡唑甲烷四羰基钨衍生物CH2Pz2W(CO)4]。

Modification of Bis(pyrazol-1-yl)methanes with Organotin and Their Reactions with W(CO)5THF

The modification of bis(pyrazol-1-yl)methanes by substitution of organotin groups on the methine carbon was carried out by the reaction of bis(pyrazol-1-yl)methyllithium(LiCHPz_2) with organotin halide(R_3SnX), yielding a series of R_3SnCHPz(R=alkyl or aryl; Pz=substituted pyrazole) ligands. Upon the treatment of these ligands with W(CO)_5THF, they displayed versatile reactivities, depending on the properties of substitutions on the tin atom. The reaction of Ar_3SnCHPz_2 with (W(CO)_5THF) resulted in the oxidative addition of the tin-carbon(sp~3) bond to the tungsten(0) center, while the similar reaction of Bz_3SnCHPz_2(Bz=benzyl; Pz=3,5-dimethylpyrazole) only gave decarbonylation complex of (\Bz_3Sn\5)(CHPz_2W(CO)_4\]). In addition, the reactions of Ph_2BzSnCHPz_2 and (PhMe_2CCH_2)_3SnCHPz_2 with (W(CO)_5THF) resulted in the partial decomposition of ligands to yield CH_2Pz_2W(CO)_4 and \, with the loss of organotin groups.