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.
张晓燕
,
宋海滨
,
唐良富
. 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[J]. 化学学报, 2011
, 69(21)
: 2567
-2573
.
DOI: 10.6023/A1103311B
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(3,5- Me2Pz)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-#em/em#) 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 product (PhO)2PCH(3,5-Me2Pz)2Mo(CO)3, besides the substituted reaction of the carbonyl group.
