Phosphaisonitrile umpolung – synthesis and reactivity of chloro aminophosphino carbynes
| Autor: | Anthony F. Hill, Benjamin J. Frogley, Annie L. Colebatch |
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| Rok vydání: | 2019 |
| Předmět: | |
| Zdroj: | Dalton Transactions. 48:10628-10641 |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/c9dt01838g |
| Popis: | Sequential treatment of [W([triple bond, length as m-dash]CBr)(CO)2(Tp*)] (Tp* = hydrotris(dimethylpyrazolyl)borate) with nBuLi and Cl2PNiPr2 provides the aminochlorophosphinocarbyne [W([triple bond, length as m-dash]CPClNiPr2)(CO)2(Tp*)]. The chloro substituent undergoes subsitution with RLi (R = Me, Et, Ph) to afford [W([triple bond, length as m-dash]CPRNiPr2)(CO)2(Tp*)] and with [W([triple bond, length as m-dash]CLi)(CO)2(Tp*)] to give the aminobis(alkylidynyl)phosphine [iPr2NP{C[triple bond, length as m-dash]W(CO)2(Tp*)}2]. Treatment with Li[BHEt3] gives the primary aminophosphine [W([triple bond, length as m-dash]CPHNiPr2)(CO)2(Tp*)], formed in a mixture with the ethyl derivative [W([triple bond, length as m-dash]CPEtNiPr2)(CO)2(Tp*)]. Although they could not be isolated, spectroscopic data indicated that halide abstraction with Al2Cl6 forms the phosphaisonitrile salt [W(CPNiPr2)(CO)2(Tp*)][AlCl4], which displays electrophilic character at phosphorus, e.g., in the reaction with diphenylacetylene to furnish the phosphirenium salt [W{CP(C2Ph2)NiPr2}(CO)2(Tp*)][AlCl4]. Finally, the reaction with LiNPh2 gives the mixed diaminophosphinocarbyne, [W{[triple bond, length as m-dash]CP(NiPr2)(NPh2)}(CO)2(Tp*)]. |
| Databáze: | OpenAIRE |
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