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Insertion of the N,B,N-chelated germylene into P-Cl Bond(s) in selected chlorophosphines
Authors: Böserle Jiří | Jambor Roman | Růžička Aleš | Dostál Libor
Year: 2018
Type of publication: článek v odborném periodiku
Name of source: Journal of Organometallic Chemistry
Publisher name: Elsevier Science BV
Place: Amsterdam
Page from-to: 44-50
Titles:
Language Name Abstract Keywords
cze Inserce N,B,N-chelatovaného germylénu do vazby P-Cl N,B,N-chelatovaného germylénu [(i-Pr)(2)NB(NDmp)(2)]Ge (1) (Dmp = 2,6-Me2C6H3) reagoval s Ph2PCl za vzniku [(i-Pr)2NB(NDmp)(2)]Ge(PPh2)Cl (2). Inserce; N,B,N-chelatovaného; germylénu; vazby; P-Cl
eng Insertion of the N,B,N-chelated germylene into P-Cl Bond(s) in selected chlorophosphines The reaction of the N,B,N-chelated germylene [(i-Pr)(2)NB(NDmp)(2)]Ge (1) (where Dmp = 2,6-Me2C6H3) with Ph2PCl in 1:1 stoichiometric ratio led to a smooth insertion into the P-Cl bond under formation of [(i-Pr) 2NB(NDmp)(2)]Ge(PPh2)Cl (2). Similarly, the treatment of 1 with RPCl2 in 2:1 stoichiometric ratio resulted in double insertion products {[(i-Pr)(2)NB(NDmp)(2)]GeCl}(2)(PR) [where R = Ph (3) or t-Bu (4)]. The products were characterized by H-1, C-13{H-1} and P-31{H-1} NMR spectroscopy and in the case of 2 and 4 by single-crystal X-ray diffraction analysis. During an initial attempt to crystallize 4, single-crystals of its decomposition product {[(i-Pr)(2)NB(NDmp)(2)]GeCl}{[(i-Pr)(2)NB(NDmp)(NHDmp)]GeCl2}(Pt-Bu) (5) were fortuitously isolated and its structure was determined by X-ray diffraction analysis and in solution by NMR studies. The attempt to synthesize compound 5 in a controlled manner by the reaction of 4 with one equiv. of HCl led to the mixture of 5 and {[(i-Pr)(2)NB(NDmp)(NHDmp)]GeCl2}(2)(Pt-Bu) (6) that could be separated by a fractional crystallization. Germylenes; Bis(amino)boranes; Insertion reaction; Group 14 elements; Oxidative addition

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