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Rare Earth Complexes of Bulky 2,6‐Diphenylphenolates Containing Additional, Potentially Buttressing 3,5‐Substituents
Author(s) -
Deacon Glen B.,
Fanwick Phillip E.,
Gitlits Alex,
Rothwell Ian P.,
Skelton Brian W.,
White Allan H.
Publication year - 2001
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(200106)2001:6<1505::aid-ejic1505>3.0.co;2-v
Subject(s) - homoleptic , chemistry , tetrahydrofuran , trigonal bipyramidal molecular geometry , ligand (biochemistry) , transmetalation , medicinal chemistry , stereochemistry , metal , redox , crystallography , crystal structure , inorganic chemistry , catalysis , organic chemistry , biochemistry , receptor , solvent
The rare earth aryloxide complexes, [Yb(OAr t Bu ) 3 (THF)]·THF, [Sc(OAr t Bu ) 3 (THF)]·THF, [Yb(OAr Me ) 3 (THF)], and [Sm(OAr Ph ) 3 (THF) 2 ] (OAr R = 2,6‐diphenyl‐3,5‐di‐R‐phenolate), have been prepared by redox transmetallation/ligand exchange between the rare earth metal, bis(pentafluorophenyl)mercury, and HOAr R in tetrahydrofuran. This reaction also provided [Yb(OAr Ph ) 3 (DME)]·3/2THF by incorporation of adventitious 1,2‐dimethoxyethane. A similar reaction between Yb metal, diphenylmercury, and HOAr Me gave [Yb(OAr Me ) 2 (THF) 3 ]. The homoleptic complexes [Yb(OAr Ph ) 3 ] and [Sc(OAr H ) 3 ] have been prepared by direct reaction of the rare earth element with HOAr R in a sealed tube in the presence of mercury at elevated temperatures (200−250 °C) and the latter was converted into [Sc(OAr H ) 3 (THF)] by treatment with THF. X‐ray crystal structure determinations of [Yb(OAr t Bu ) 3 (THF)]·THF, [Sc(OAr t Bu ) 3 (THF)]·THF, and [Yb(OAr Me ) 3 (THF)] show the complexes to be monomeric and four coordinate with a trigonal pyramidal stereochemistry. These structures provide clear evidence that groups meta to the phenolate donor can modify the coordination behaviour of the 2,6‐diphenylphenolate ligand. In [Yb(OAr Ph ) 3 (DME)]·3/2THF a distorted square pyramidal stereochemistry is observed. The divalent complex [Yb(OAr Me ) 2 (THF) 3 ] exhibits a distorted trigonal bipyramidal arrangement of the oxygen donor atoms with apical THF ligands. The homoleptic scandium 2,6‐diphenylphenolate has three oxygen atoms in a triangular array with additional π‐η 1 ‐Ph ··· Sc interactions above and below the ScO 3 plane [C−Sc−C = 154.2(8)°], providing a new type of binding of this aryloxide ligand.