排序方式: 共有4条查询结果,搜索用时 31 毫秒
1
1.
Matthias Seibert 《Journal of organometallic chemistry》2003,687(1):131-141
The P-functional organotin chloride Ph2PCH2CH2SnCl3 reacts with [(COD)MCl2] and trans-[(Et2S)2MCl2] (M=Pd, Pt) in molar ratio 1:1 to the zwitterionic complexes [(COD)M+(Cl)(PPh2CH2CH2Sn−Cl4)] (1: M=Pd; 2: M=Pt) and trans-[(Et2S)2M+(Cl)(PPh2CH2CH2Sn−Cl4)] (3: M=Pd; 4: M=Pt). The same reaction with [(COD)Pd(Cl)Me] yields under transfer of the methyl group from palladium to tin the complex [(COD)M+(Cl)(PPh2CH2CH2Sn−MeCl3)] (5) which changes in acetone into the dimeric adduct [Cl2Pd(PPh2CH2CH2SnMeCl2·2Me2CO)]2 (6). In molar ratio 2:1 Ph2PCH2CH2SnCl3 reacts with [(COD)MCl2] to the complexes [Cl2Pd(PPh2CH2CH2SnCl3)2] (7: M=Pd, mixture of cis/trans isomer; 8: M=Pt, cis isomer). In a subsequent reaction 8 is transformed in acetone into the 16-membered heterocyclic complex cis-[Cl2Pt(PPh2CH2CH2)2SnCl2]2 (9). trans-[(Et2S)2PtCl2] and Ph2PCH2CH2SnCl3 in molar ratio 1:2 yields the zwitterionic complex [(Et2S)M+(Cl)(PPh2CH2CH2SnCl3)(PPh2CH2CH2Sn−Cl4)] (10). The results of crystal structure analyses of 1, 3, 6, 9 and of the adduct of the trans-isomer of 7 with acetone (7a) are reported. 31P- and 119Sn-NMR data of the complexes are discussed. 相似文献
2.
Vadim V. Negrebetsky Peter G. Taylor Aleksander G. Shipov Yuri E. Ovchinnikov Allen Bowden Yuri I. Baukov 《Journal of organometallic chemistry》2008,693(7):1309-1320
The novel compounds, N-(trifluorosilylmethyl)-[N-(S)-(1-phenylethyl)]-acetamide (1a) and 1-(trifluorosilylmethyl)-2-oxoperhydroazepine (1b) have been prepared from the corresponding NH-compounds using ClCH2SiCl3/Et3N or ClCH2SiCl3/(Me3Si)2NH followed by methanolysis or hydrolysis of the reaction mixture in the presence of Lewis bases, and then BF3 etherate. Potassium-(18-crown-6)-(2-oxoperhydroazepinomethyl)tetrafluorosilicate (2) was synthesized by reaction of the trifluoride (1b) with KF in the presence of 18-crown-6. Using 19F, 29Si NMR and X-ray diffraction techniques it was established that the silicon atom is pentacoordinate in the trifluorides (1a, b) and hexacoordinate in the adduct 2. Thus the internal coordination of the O → Si bond present in the trifluoride (1b) is retained in the adduct 2.The stereochemical non-rigidity of the trifluorides (1a, b) and the N-(trifluorosilylmethyl)-N-methylacetamide (1c) was investigated using dynamic 19F NMR spectroscopy. The activation barriers for permutational isomerization are in the range 9.5-10 kcal mol−1. Lower values of ΔG# for permutation of trifluorides (1a-c) compared to the monofluorides with the coordination core OSiC3F together with small negative values for the activation entropy implies a non-dissociative mechanism. Quantum-chemical analysis suggests a mechanism involving a turnstile rotation. 相似文献
3.
Matthias Seibert Kurt Merzweiler Christoph Wagner Horst Weichmann 《Journal of organometallic chemistry》2002,650(1-2):25-36
The P-functional organotin dichloride [Ph2P(CH2)3]2SnCl2 (3) is synthesized by reaction of Ph2P(CH2)3MgCl with SnCl4 independently of the molar ratio of the starting compounds. The corresponding organotin trichlorides Ph2P(CH2)nSnCl2R (4: n=2, R=Cl; 5: n=3, R=Cl; 6: n=3, R=Me) are formed in a cleavage reaction of Ph2P(CH2)nSnCy3 (n=2, 3) with SnCl4 or MeSnCl3, respectively. The main features of the crystal structures of 3–6 are both intra- and intermolecular PSn coordinations and the existence of intermolecular Sn---ClSn bridges. For further characterization of the title compounds, the adducts 4(Ph3PO)2 (7) and 5(Ph3PO) (8), as well as the P-oxides and P-sulfides of 3–6 (9–15), are synthesized. The results of crystal structure analyses of 7, 11, 12, and 14 are reported. The structures of 9–15 are characterized by intramolecular P=XSn interactions (X=O, S). A first insight into the structural behavior of the compounds 3–15 in solution is discussed on the basis of multinuclear NMR data. 相似文献
4.
Oliver Seiler Christian Burschka Kathrin Götz Martin Kaupp Stefan Metz Reinhold Tacke Prof. Dr. 《无机化学与普通化学杂志》2007,633(15):2667-2670
The λ6Si‐silicate [K(18‐crown‐6)]2[Si(NCO)6] ( 10 ) was synthesized by treatment of Si(NCO)4 with KNCO in the presence of 18‐crown‐6. Compound 10 (SiN6 skeleton) is the first example of a hexa(cyanato‐N)silicate. It was characterized by solid‐state and solution NMR spectroscopy, and the acetonitrile solvate 10· 2CH3CN was studied by single‐crystal X‐ray diffraction. To differentiate between the two isomeric [Si(NCO)6]2? and [Si(OCN)6]2? dianions, computational studies were performed. 相似文献
1