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Lewis Base Stabilized Phosphanylborane
Author(s) -
Schwan KarlChristian,
Timoskin Alexey Y.,
Zabel Manfred,
Scheer Manfred
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600185
Subject(s) - chemistry , lewis acids and bases , trimethylamine , alkane stereochemistry , crystal structure , crystallography , lone pair , density functional theory , stereochemistry , monomer , sulfur , medicinal chemistry , molecule , computational chemistry , organic chemistry , polymer , catalysis
The abstraction of the Lewis acid from [W(CO) 5 (PH 2 BH 2 ⋅NMe 3 )] ( 1 ) by an excess of P(OMe 3 ) 3 leads to the quantitative formation of the first Lewis base stabilized monomeric parent compound of phosphanylborane [H 2 PBH 2 ⋅NMe 3 ] 2 . Density functional theory (DFT) calculations have shown a low energetic difference between the crystallographically determined antiperiplanar arrangement of the lone pair and the trimethylamine group relative to the PB core and the synperiplanar conformation. Subsequent reactions with the main‐group Lewis acid BH 3 as well as with an [Fe(CO) 4 ] unit as a transition‐metal Lewis acid led to the formation of [(BH 3 )PH 2 BH 2 ⋅NMe 3 ] ( 3 ), containing a central H 3 BPH 2 BH 2 unit, and [Fe(CO) 4 (PH 2 BH 2 ⋅NMe 3 )] ( 4 ), respectively. In oxidation processes with O 2 , Me 3 NO, elemental sulfur, and selenium, the boranylphosphine chalcogenides [H 2 P(Q)BH 2 ⋅NMe 3 ] (Q = S 5 b ; Se 5 c ) as well as the novel boranyl phosphonic acid [(HO) 2 P(O)BH 2 ⋅NMe 3 ] ( 6 a ) are formed. All products have been characterized by spectroscopic as well as by single‐crystal X‐ray structure analysis.