Abstract
The polycyclic Group 14 amides [P(μ-N t Bu) 2P( t BuN) 2]M, M = Ge ( 4), Sn ( 5) were synthesized from cis-[P(μ-N t Bu) 2P( t BuNLi · THF) 2] and GeCl 2 · dioxane or SnCl 2, respectively. Oxidation of these heterocarbenoids or of the analogous diazastannylene [MeSi(μ- t BuN) 2SiMe( t BuN) 2]Sn with O 2, S 8 and Se n furnished the chalcogenides {[P(μ-N t Bu) 2P( t BuN) 2]GeO} 2 ( 6), {[P(μ-N t Bu) 2P( t BuN) 2]SnE} 2, E = O ( 7), S ( 8), Se ( 9), {[SP(μ-N t Bu) 2P( t BuN) 2]SnS} 2 ( 10), and {[MeSi(μ- t BuN) 2SiMe( t BuN) 2]SnE} 2, E = S ( 11), Se ( 12), respectively. All products ( 6– 12) were shown by single-crystal X-ray methods to consist of dimeric molecules with central (M–E) 2 rings, M = Group 14 element, E = chalcogen. The exclusive formation of dimeric compounds with bridging M–E–M bonds, vs. alternative monomeric structures with terminal M E bonds, is rationalized in terms of the thermodynamic favorability of the dimers. The case is made that most, if not all, currently known Group 14 chalcogenides, even those labeled “kinetically stabilized”, are really thermodynamic products.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
