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A Bicyclic P–P‐Bridged 1,3,2,4‐Diphosphadiboretane Cation and an Imino(phosphinidene)borane–AlBr 3 Adduct
Author(s) -
Knabel Klaus,
Klapötke Thomas M.,
Nöth Heinrich,
Paine Robert T.,
Schwab Ingo
Publication year - 2005
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/ejic.200400372
Subject(s) - chemistry , phosphinidene , natural bond orbital , adduct , bicyclic molecule , allene , phosphonium , borane , medicinal chemistry , stereochemistry , crystallography , computational chemistry , density functional theory , polymer chemistry , organic chemistry , catalysis
Depending on reaction conditions the 1,3,2,4‐diphosphadiboretane 1 reacts with AlBr 3 to give the unstable adduct tmp=B=P( t Bu)AlBr 3 , 3 , and/or the somewhat more stable salt [(tmpB) 2 (P t Bu)P] + [AlBr 4 ], 2 . The X‐ray structure determination of 3 shows an almost linear NBP array with BN and BP double bonds resembling an allene type structure. NBO analysis shows the presence of BN‐ and BP‐π‐bonds. On the other hand, the cation of compound 2 has a bicyclic structure with a long P–P bond [2.349(2) Å]. The B–P bonds to the phosphonium type P2 atom [av. 1.939(5) Å] are longer than those to the tri‐coordinated P1 atom [1.889(6) Å]. NBO analysis of the model compound (H 2 NB) 2 (PMe)P + , 9 , show that the P–P bond in 2 is formed from p ‐orbitals. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)