Conceptual basis of the selective activation of bis(dialkylamino)methoxyphosphines by weak acids and its application toward the preparation of deoxynucleoside phosphoramidites in situ
Synthesis by the Arbuzov-like dealkylation reaction, characterization, and reactivity of phosphonate and amino-substituted phosphonate ruthenium complexes, [(η5-C5H5)(CO)2Ru{P(O)(OR) (NC4H8) 2−}] (n = 0–2), and comparison with the iron analogues
shows no reaction. The comparison of spectroscopic data of [Cp(CO)2ML]+ and Cp(CO)2MP(O)(OR)n(NC4H8)2–n} (M Fe, Ru) reveals that Mδ+-Pδ− polarization is greater for Ru than Fe. Cp(CO)2RuP(O)(NC4H8)2} shows an NC4H8/OR exchange reaction in ROH at 65°C for 5 h to give CP(CO)2RuP(O)(OR)(NC4H8)}, whereas the corresponding iron complex shows no reaction. The exchange reaction of the Ru complex proceeds
Cp(CO)2 RuCl与具有OR基团和/或吡咯烷基的三价磷化合物(L)(LP(OR)n(NC 4 H 8)3- n(R Me,Et; n = 0–3))在室温下在苯中检测,结果表明Cl / L和CO / L交换反应同时发生,从而得到[Cp(CO)2 RuL] Cl和Cp(CO) RuClL,分别。当L为P(OR)3或P(OR)2(NC 4 H 8)时,还形成[Cp(CO)RuL 2 ] Cl。[CP(CO)2 RUL] +分离为BF 4 -盐在CP的反应(CO)良好的产率2的RuCl用的AgBF 4和L,当L为P(OR)3或P(OR)2(NC 4 H ^ 8),并被分离为氯-治疗的盐当L为P(OR)NC 4 H 8)2或P(NC 4 H 8)3时与L配合使用。用Et 4 NCl处理[Cp(CO)2 RuL] BF 4或回流[Cp(CO)2 RuL] Cl的苯溶液进行类似Arbuzov
Conversion of cationic phosphite complexes into phosphonate complexes with selective deamination on the coordinating phosphorus. Reaction of [(η5-C5H5)L2Fe{P(NC4H8)n(OMe)3−n}]+ (LCO, PMe3) with KOH to afford (η5-C5H5)L2Fe{P(O)(NC4H8)n−1(OMe)3−n}
Amino-substituted phosphite iron complexes, [Cp(CO)2FeP(NC4H8)n(OMe)3−n}]+ (n=1−3), react with KOH in H2O at room temperature to give phosphonatecomplexes, Cp(CO)2FeP(O)(NC4H8)n−1(OMe)3−n} with selectivedeamination. The reactions with KOH of phosphitecomplexes [Cp(PMe3)2Fe(P(NC4H8)n(OMe)3−n}]+ which have no carbonyl ligands yield deaminated phosphonatecomplexes Cp(PMe3)2FeP(O)(NC4H8)n−1(OMe)3−n}, indicating