P–N and N–Mo Bond Formation Processes in the Reactions of a Pyramidal Phosphinidene-Bridged Dimolybdenum Complex with Diazoalkanes and Organic Azides
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https://figshare.com/articles/dataset/P_N_and_N_Mo_Bond_Formation_Processes_in_the_Reactions_of_a_Pyramidal_Phosphinidene-Bridged_Dimolybdenum_Complex_with_Diazoalkanes_and_Organic_Azides/12350471
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资源简介：
The reactivity of
the complex [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(CO)2(η6-HMes*)(PMe3)] (1) toward different diazoalkanes and organic azides was investigated.
The pyramidal phosphinidene ligand in 1 displayed a strong
nucleophilicity, enabling these reactions to proceed rapidly even
below room temperature. Thus, 1 reacted rapidly at 253
K with different diazoalkanes N2CRR′ (R,R′
= H,H, Ph,Ph, H,CO2Et) to give the corresponding P:P-bridged
phosphadiazadiene derivatives as major products which, however, could
not be isolated. Reaction of the latter with [H(OEt2)2](BAr′4) yielded the corresponding cationic
derivatives [Mo2Cp{μ-κ1P:κ1P,η5-P(NHNCRR′)C5H4}(η6-HMes*)(CO)2(PMe3)](BAr′4), which were isolated in ca. 70%
yield. The related species [Mo2Cp{μ-κ1P:κ1P,η5-P(NMeNCHCO2Et)C5H4}(η6-HMes*)(CO)2(PMe3)](BAr′4) was isolated upon
reaction of the ethyl diazoacetate derivative with MeI and subsequent
anion exchange with Na(BAr′4). Reaction of 1 with aryl azides (4-C6H4Me)N3 and (4-C6H4F)N3 proceeded rapidly
at low temperature to give possibly the corresponding P:P-bridged
phosphaimine derivatives as major products, which could be neither
isolated. Protonation of these products with [H(OEt2)2](BAr′4) gave the corresponding aminophosphanyl
complexes [Mo2Cp{μ-κ1P:κ1P,η5-P(NHR)C5H4}(η6-HMes*)(CO)2(PMe3)](BAr′4), isolated in ca. 75% yield. In
contrast, the result of reactions of 1 with benzyl azide
was strongly dependent on temperature, including the temperature in
the subsequent methylation step that gave isolable cationic derivatives.
By a careful choice of experimental conditions, different complexes
having methylated phosphatriazadiene ligands were isolated, such as
[Mo2Cp{μ-κ1P:κ1P,η5-P(NNNMeCH2Ph)C5H4}(η6-HMes*)(CO)2(PMe3)](BAr′4) and the metallacyclic derivatives syn- and anti-[Mo2Cp{μ-κ2P,N:κ1P,η5-P(NMeNNCH2Ph)C5H4}(η6-HMes*)(CO)(PMe3)](BAr′4). Density
functional theory calculations, along with NMR monitoring experiments,
revealed that the formation of the latter products stemmed from different
and kinetically favored phosphatriazadiene intermediates, thermodynamically
disfavored with respect to the denitrogenation process, otherwise
yielding phosphaimine derivatives.
创建时间：
2020-05-21
