A detailed method for the preparation of [Cp'' Zr(η -P )] (1) is presented. The coordination behavior of 1 towards Lewis acidic transition metal complexes of tungsten, manganese, and iron, respectively, and main group compounds (AlMe , AlEt ) was investigated in detail by computational and experimental studies. In doing so, a series of unprecedented complexes with different coordination modes and multiple coordination numbers of the tetraphosphabicyclo[1.1.0]butane framework were synthesized. All products, as well as the starting materials, were comprehensively characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single crystal X-ray structural analysis.
The Sn/P cage compounds [Sn 10 (tBuP) 4 ] (1) and [Sn 10 (tBuP) 7 Cl 4 ] (2) were obtained by the reaction of LitBuPH with SnBr 2 and SnCl 2 , respectively. Theoretical calculations confirm that the tin atoms in 2 feature different formal oxidation states. The reaction of PbCl 2 with LitBuPH and LiPHSiiPr 3 yields the Pb/P cage com-* Prof. Dr. M. Scheer 1739 pounds [Pb 7 (tBuP) 7 ] (3) and [Pb 6 (PSiiPr 3 ) 6 ] (4), respectively, that represent new derivatives of known polyhedrons of this class of compounds. The new products were characterized by X-ray diffraction, elemental analysis and partially by MS and MAS-NMR spectroscopy.nations of Sn/P [3] and Pb/P. [4] For the latter only few examples exist, which is also true for corresponding Ge/P systems. [5] Depending on the used synthetic method and steric requirements of the adjacent substituents, different polyhedrons are obtained. Usually, cubes and hexagonal prismatic structures dominate as shown in type A and B compounds for M 4 (PR) 4 and M 6 (PR) 6 derivatives. For the composition M 7 (PR) 7 compounds of type C are known, whereas by using a thermal condensation reaction of R 2 Ge(PH 2 ) 2 compound D was synthesized. [6] A first mixed valence cage E was obtained by von Hänisch et al. by the reaction of SnCl 2 with Li 2 P(SiPr 3 ). [7] Published synthetic procedures involve reactions between RPH 2 or LiHPR and e.g. Sn(NMe 2 ) 2 [3,8] or LiCl elimination reactions that use the double lithiated species RPLi 2 and dihal-M. Scheer et al.
The missing member [Cp′′2Zr(η2‐P3CtBu)] (Cp′′=η5‐C5H3tBu2) of the phosphorus‐containing bicyclobutane zirconium complex family was synthesized by reaction between tetraphosphazirconocene derivative [Cp′′2Zr(η2‐P4)] and a phosphaalkyne with the release of a formal P2 unit. Synthetic evidence of another unknown isomer [Cp′′2Zr(η2‐P2(CtBu)2)] was found; according to DFT calculations, it is the stable form if a Cp′′2Zr moiety is used.
The use of [Cp′′2Zr(η1:1‐E4)] (E=P (1 a), As (1 b), Cp′′=1,3‐di‐tert‐butyl‐cyclopentadienyl) as phosphorus or arsenic source, respectively, gives access to novel stable polypnictogen transition metal complexes at ambient temperatures. The reaction of 1 a/1 b with [CpRNiBr]2 (CpR=CpBn (1,2,3,4,5‐pentabenzyl‐cyclopentadienyl), Cp′′′ (1,2,4‐tri‐tert‐butyl‐cyclopentadienyl)) was studied, to yield novel complexes depending on steric effects and stoichiometric ratios. Besides the transfer of the complete En unit, a degradation as well as aggregation can be observed. Thus, the prismane derivatives [(Cp′′′Ni)2(μ,η3:3‐E4)] (2 a (E=P); 2 b (E=As)) or the arsenic containing cubane [(Cp′′′Ni)3(μ3‐As)(As4)] (5) are formed. Furthermore, the bromine bridged cubanes of the type [(CpRNi)3{Ni(μ‐Br)}(μ3‐E)4]2 (CpR=Cp′′′: 6 a (E=P), 6 b (E=As), CpR=CpBn: 8 a (E=P), 8 b (E=As)) can be isolated. Here, a stepwise transfer of En units is possible, with a cyclo‐E42− ligand being introduced and unprecedented triple‐decker compounds of the type [{(CpRNi)3Ni(μ3‐E)4}2(μ,η4:4‐E′4)] (CpR=CpBn, Cp′′′; E/E′=P, As) are obtained.
Das vermisste Mitglied [Cp′′2Zr(η2‐P3CtBu)] (Cp′′=η5‐C5H3tBu2) der P enthaltenden Bicyclobutanzirconiumkomplexe wurde aus dem Zirconocen‐Derivat [Cp′′2Zr(η2‐P4)] und einem Phosphaalkin unter formaler Eliminierung einer P2‐Einheit erhalten. Weiterhin konnten präparative Anhaltspunkte für das bisher unbekannte Isomer [Cp′′2Zr(η2‐P2(CtBu)2)] erhalten werden, nach DFT‐Rechnungen das stabile Isomer, wenn ein Cp′′2Zr‐Fragment verwendet wird.
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