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Phosphacarborane Chemistry: The Synthesis of the Parent Phosphadicarbaboranes nido ‐7,8,9‐PC 2 B 8 H 11 and [ nido ‐7,8,9‐PC 2 B 8 H 10 ] − , and Their 10‐Cl Derivatives − Analogs of the Cyclopentadienide Anion
Author(s) -
Štíbr Bohumil,
Holub Josef,
Bakardjiev Mario,
Hnyk Drahomír,
Tok Oleg L.,
Milius Wolfgang,
Wrackmeyer Bernd
Publication year - 2002
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 - 10.1002/1099-0682(200209)2002:9<2320::aid-ejic2320>3.0.co;2-e
Subject(s) - chemistry , deprotonation , dichloromethane , carborane , chemical shift , basis set , protonation , ab initio , naphthalene , computational chemistry , medicinal chemistry , hydrolysis , ion , crystallography , stereochemistry , solvent , organic chemistry , density functional theory
The reaction of the carborane nido ‐5,6‐C 2 B 8 H 12 ( 1 ) with PCl 3 in dichloromethane in the presence of a “proton sponge” [PS = 1,8‐bis(dimethylamino)naphthalene], followed by hydrolysis of the reaction mixture, resulted in the isolation of the eleven‐vertex nido ‐phosphadicarbaboranes 7,8,9‐PC 2 B 8 H 11 ( 2 ) and 10‐Cl‐7,8,9‐PC 2 B 8 H 10 ( 10‐Cl‐2 ), depending on the ratio of the reactants. Both of these compounds can be deprotonated by PS to give the nido anions [7,8,9‐PC 2 B 8 H 10 ] − ( 2 − ) and [10‐Cl‐7,8,9‐PC 2 B 8 H 9 ] − ( 10‐Cl‐2 − ). The molecular geometries of all compounds were optimized by ab initio methods at a correlated level of theory [RMP2(fc)] using the 6‐31G* basis set and their correctness was assessed by a comparison of the experimental 11 B NMR chemical shifts with those calculated by the GIAO‐SCF/II//RMP2(fc)/6‐31G* method. Moreover, the structure of 10‐Cl‐2 − was determined by an X‐ray diffraction analysis. The anionic compounds 2 − and 10‐Cl‐2 − are analogs of the Cp (Cp = η 5 ‐C 5 H 5 − ) anion. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)