%0 Generic
%A Becker, Gerd
%A Brombach, Heike
%A Horner, Stephen T.
%A Niecke, Edgar
%A Schwarz, Wolfgang
%A Streubel, Rainer
%A Würthwein, Ernst-Ulrich
%D 2005
%T Synthesis and Structure of K+[iPrNCP]-, a
1-Aza-3λ3-phospha-3-allenide†
%U https://acs.figshare.com/articles/dataset/Synthesis_and_Structure_of_K_sup_sup_i_sup_i_sup_i_sup_sup_PrN_C_P_sup_sup_a_1_Aza_3_sup_3_sup_phospha_3_allenide_sup_sup_/3373936
%R 10.1021/ic048162+.s001
%2 https://acs.figshare.com/ndownloader/files/5217412
%K λ 3
%K quantum chemical calculations
%K potassium
%K anion
%K phosphaalkyne 1
%X 2-Isopropyl(trimethylsilyl)amino-1λ3-phosphaalkyne 1 reacts with potassium tert-butoxide to form potassium 1-isopropyl-1-aza-3λ3-phospha-3-allenide (2). This compound was structurally characterized as the corresponding 18-crown-6
ether complex 3. The molecular structure of 1 was also determined in order to compare the bonding situation in
the anion and the neutral λ3-phosphaalkyne. Compound 3 contains a nitrogen−carbon−phosphorus group for which
the parameters were shown by X-ray structural analysis and quantum chemical calculations to lie between the
extrema N−C⋮P and NCP, suggesting reactivity typical of an ambident anion. This is indeed the case, as
subsequent reaction of 2 with chlorotrimethylsilane at nitrogen regenerates the λ3-phosphaalkyne 1; with
chlorotriphenylsilane the new derivative 4 is formed. In contrast, chlorotrimethylstannane reacts at phosphorus,
giving the 1-aza-3λ3-phosphaallene isopropyliminomethylidene(trimethylstannyl)phosphane 5.
%I ACS Publications