含钼(钨)锡键的四元金属有机杂环化合物的合成与反应研究

Synthesis and Reactivity of the Four-membered Heterometallacycles with M-Sn(M=Mo or W) Bonds

通过三苯基锡基-双(3,5-二甲基吡唑)甲烷与羰基钼的反应合成了钼锡键合的四元金属杂环化合物CH(3,5-Me2Pz)2Mo(CO)3SnPh3(Pz=1-吡唑基).当用叔丁基异腈处理该化合物及其钨类似物时,伴随着有机锡结构单元的丢失,金属钼(钨)上发生还原消除并分解得到化合物CH2(3,5-Me2Pz)2M(CO)3(CNBu-t)(M为Mo或W).另外,该化合物与三苯基膦或亚磷酸甲酯及异丙酯反应时,只发生羰基取代反应得到化合物CH(3,5-Me2Pz)2Mo(CO)2(PR3)SnPh3(R为苯基、甲氧基及异丙氧基).而用亚磷酸苯酯与之反应,除得到羰基取代产物外,还伴随着P—O/C键的交换,得到金属钼上还原消除的产物(PhO)2PCH(3,5-Me2Pz)2Mo(CO)3.

Four-membered heterometallacylic complex CH（3,5-Me2Pz）2Mo（CO）3SnPh3（Pz=pyrazol-1-yl） has been obtained by the reaction of Ph3SnCH（3,5-Me2Pz）2 with Mo（CO）6.Treatment of this complex and its tungsten analog with CNBu-t resulted in the reductive elimination reaction to give complexes CH2（3,5Me2Pz）2M（CO）3（CNBu-t）（M=Mo or W） with the loss of organotin fragment.In addition,reaction of this complex with PR3（R=Ph,OMe or OPr-i） only yielded complexes CH（3,5-Me2Pz）2Mo（CO）2（PR3）SnPh3.While the similar reaction with P（OPh）3 led to the P-O/C exchange to give the reductive elimination prod-uct（PhO）2PCH（3,5-Me2Pz）2Mo（CO）3,besides the substituted reaction of the carbonyl group.