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(H 2 Si) 2 E 2 and (Mes( t Bu)Si) 2 E 2 (E = As, P): Incommensurable Systems of Different Stability with Unusually Long EE Bonds
Author(s) -
Driess Matthias,
Janoschek Rudolf,
Pritzkow Hans
Publication year - 1992
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199204601
Subject(s) - butane , photodissociation , quantum chemical , chemistry , inversion (geology) , crystallography , stereochemistry , catalysis , photochemistry , molecule , organic chemistry , paleontology , structural basin , biology
Unexpectedly kinetically stable is exo, endo ‐1,3‐diarsa‐2,4‐disilabicyclo[1.1.0]‐butane ( 1a ) in comparison to its phosphorus homologue 2a . Compound 1a , accessible by the photolysis of the 1,3‐dimercurio derivative 3 , is converted only slowly into 1b ( exo,exo ). The most notable feature of 1b is its unusually long As‐As bond (2.602(3) Å). Quantum chemical calculations showed that as a result of their bulky substituents 1 and 2 cannot undergo Si inversion like their unsubstituted parent compounds. R 1 = t Bu, R 2 = 2,4,6‐C 6 H 2 Me 3