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Crystalline Diuranium Phosphinidiide and μ‐Phosphido Complexes with Symmetric and Asymmetric UPU Cores
Author(s) -
Rookes Thomas M.,
Gardner Benedict M.,
Balázs Gábor,
Gregson Matthew,
Tuna Floriana,
Wooles Ashley J.,
Scheer Manfred,
Liddle Stephen T.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201706002
Subject(s) - chemistry , steric effects , ether , crystallography , stereochemistry , medicinal chemistry , organic chemistry
Reaction of [U(Tren TIPS )(PH 2 )] ( 1 , Tren TIPS =N(CH 2 CH 2 NSiPr i 3 ) 3 ) with C 6 H 5 CH 2 K and [U(Tren TIPS )(THF)][BPh 4 ] ( 2 ) afforded a rare diuranium parent phosphinidiide complex [{U(Tren TIPS )} 2 (μ‐PH)] ( 3 ). Treatment of 3 with C 6 H 5 CH 2 K and two equivalents of benzo‐15‐crown‐5 ether (B15C5) gave the diuranium μ‐phosphido complex [{U(Tren TIPS )} 2 (μ‐P)][K(B15C5) 2 ] ( 4 ). Alternatively, reaction of [U(Tren TIPS )(PH)][Na(12C4) 2 ] ( 5 , 12C4=12‐crown‐4 ether) with [U{N(CH 2 CH 2 NSiMe 2 Bu t ) 2 CH 2 CH 2 NSi(Me)(CH 2 )(Bu t )}] ( 6 ) produced the diuranium μ‐phosphido complex [{U(Tren TIPS )}(μ‐P){U(Tren DMBS )}][Na(12C4) 2 ] [ 7 , Tren DMBS =N(CH 2 CH 2 NSiMe 2 Bu t ) 3 ]. Compounds 4 and 7 are unprecedented examples of uranium phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.