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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2295-2299 
    ISSN: 1434-1948
    Keywords: Lewis acids ; Bismuth ; Aluminum ; Phosphorus ; Tin ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dilithium salts of N-methyl-N′,N′′-bis(diisopropyl)- and -(trimethylsilyl)-diethylenetriamine 1a,b react with SnCl2 affording the corresponding stannylenes 2a,b in 60 and 80% yield, respectively. Compound 1b also reacts with BiCl3 to give the bismuth chloride 5 (90% yield). Derivatives 2b and 5 have a symmetrical bicyclic structure and are monomeric both in solution and in the solid state. When 2b is treated with BiCl3 or PCl3, an oxidation reaction leads to the hypercoordinated tin(IV) dichloride 3 (58% yield), or a transmetallation gives rise to the oniophosphane 4 (95% yield), respectively. Transmetalation reactions also occurred when 5 was treated with AlCl3, GaCl3 or SnCl2 affording the corresponding aluminum chloride 6 (81% yield), gallium chloride 7 (38% yield) or tin dichloride 3 (38% yield). The observed reactivity for 2 and 5 is compared to that reported for Veith's stannylene or bismuth chloride.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 173-178 
    ISSN: 1434-1948
    Keywords: P Ligands ; N Ligands ; Copper ; Zinc ; Structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithiation of triphenyl(trimethylsilylimino)phosphorane Ph3P=NSiMe3 with MeLi gives the ortho-metallated species [Li(o-C6H4PPh2NSiMe3)]2·Et2O (1), which exhibits all the requirements of an organometallic ligand capable of side-arm donation. The deprotonated ortho-phenyl carbon atom gives access to metal-carbon σ bonds in transmetallation reactions, while the Ph2P=NSiMe3 moiety can donate to the same metal center through the imine nitrogen atom. In transmetallation reactions with CuBr, the dimeric organocopper complex [Cu(o-C6H4PPh2NSiMe3)]2 (2) is obtained, while application of ZnCl2 yields the monomeric zinc complex [Zn(o-C6H4PPh2NSiMe3)2] (3). Reaction with CuCl2 gives access to the new diiminophosphorane (o-C6H4PPh2NSiMe3)2 (4) through oxidative coupling at the ortho positions. In all the metal complexes, the Ph2P=NSiMe3 residue acts as a side-arm donating group through the nitrogen atom. The intermolecular N→Cu donor bond in 2 is as short as copper-amide bonds, while the N→Zn bond lengths in 3 are in the region normally found for donor bonds. Compound 4 is a molecule, possessing two Ph2P=NSiMe3 moieties bridged by a biphenylene group.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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