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The Dramatic Influence of Diamidoamine Ligands on the Structure and Reactivity of Low‐Valent Tin and Bismuth Derivatives
Author(s) -
Fauré JeanLuc,
Gornitzka Heinz,
Réau Régis,
Stalke Dietmar,
Bertrand Guy
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199912)1999:12<2295::aid-ejic2295>3.0.co;2-f
Subject(s) - chemistry , bismuth , tin , reactivity (psychology) , inorganic chemistry , organic chemistry , medicine , alternative medicine , pathology
The dilithium salts of N ‐methyl‐ N′,N′′‐ bis(diisopropyl)‐ and ‐(trimethylsilyl)‐diethylenetriamine 1a , b react with SnCl 2 affording the corresponding stannylenes 2a,b in 60 and 80% yield, respectively. Compound 1b also reacts with BiCl 3 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 BiCl 3 or PCl 3 , 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 AlCl 3 , GaCl 3 or SnCl 2 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.