Abstract: | Acyl- and Alkylidenephosphanes. XXXV. Bis N -(trimethylsilyl)iminobenzoyl]phosphanides of Lithium and Zinc – Syntheses as well as NMR Spectroscopic, Structural, and Quantumchemical Studies From the reaction of bis(tetrahydrofuran)lithium bis(trimethylsilyl)phosphanide with two equivalents of benzonitrile in 1,2-dimethoxyethane, the yellow dme complex ( 2 a ) of lithium bisN-(trimethylsilyl)iminobenzoyl]phosphanide ( 2 ) was obtained in 69% yield. However, the intermediate {1-N-lithium-N-(trimethylsilyl)amido]benzylidene}trimethylsilylphosphane ( 1 ), formed by an analogous 1 : 1 addition in diethyl ether, turned out to be unstable and as a consequence could be characterized by nmr spectroscopic methods only; attempts to isolate the compound failed, but small amounts of the neutral complex 2 b , with the ligands benzonitrile and tetrahydrofuran coordinated to lithium, precipitated. The reaction of compound 2 with zinc(II) chloride in diethyl ether gives the orange-red spiro-complex zinc bis{bisN-(trimethylsilyl)iminobenzoyl]phosphanide} ( 3 ); this complex is also formed from bisN-(trimethylsilyl)iminobenzoyl]phosphane ( 4 ), easily amenable by a lithium hydrogen exchange of 2 a with trifluoroacetic acid 18], and zinc bisbis(trimethylsilyl)amide]. As derived from nmr spectroscopic studies and x-ray structure determinations, compounds 2 a {δ31P +63.3 ppm; P21/n; Z = 4; R1 = 0.067}, 2 b {δ31P +63.3 ppm; P21/c; Z = 4; R1 = 0.063}, 3 {δ31P +58.2 ppm; C2/c; Z = 4; R1 = 0.037} and 4 {δ31P +58.1 ppm 18]} exist as cyclic 3-imino-2λ3σ2-phosphapropenylamides and -propenylamine, respectively, in solution as well as in the solid state. Unlike hydrogen derivative 4 the bisN-(trimethylsilyl)iminobenzoyl]phosphanide fragments N,N′-coordinating either a lithium or a zinc cation are characterized by almost completely equalized bond lengths; typical mean distances and angles are: P C 180.3 and 178.7; C N 130.5 and 131.8; N–Si 175.3 and 179.3; N–Li 202.3; N–Zn 203.5 pm; C P C 108.8° and 110.5°; P C N 130.9° and 132.9°; C N–Li 113.0°, C N–Zn 117.4°; N–Li–N 104.6°; N–Zn–N 108.8°. Alterations in the shape of the six membered chelate rings, caused by an exchange of the 3-imino-2λ3σ2-phosphapropenylamide or related 2λ3σ2-phospha-1,3-dionate units for the corresponding phosphorus free ligands, are discussed in detail. The results of quantumchemical DFT-B3LYP calculations coincide very well with the experimentally obtained findings. |