TY - JOUR
T1 - Axially asymmetric metal alkyls. Part 4. Synthesis and X-ray crystal structure of the tungsten(V) metallabicyclic complex [{W[(2-CH2C6H4)2]2O} 2Mg(C4H8O)4]·CH 2Cl2
AU - Engelhardt, Lutz M.
AU - Papasergio, Rocco I.
AU - Raston, Colin L.
AU - Salem, Geoffrey
AU - White, Allan H.
PY - 1986/1/1
Y1 - 1986/1/1
N2 - Reaction of the di-Grignard reagent [{Mg(thf)nCl}2{(2-CH2C6H 4)2}], derived from [Mg(anth) (thf)3] (anth = anthracene) and (2-CICH2C6H4)2, with WCI4O in tetrahydrofuran (thf) yields a paramagnetic species, shown by an X-ray diffraction study to be [{W[(2-CH2C6H4)2] 2[graphic omitted]g(thf)4]. Within each molecule the bidentate alkyl ligands have the same chirality, the overall molecular symmetry being approximately 222. A two-fold axis containing the oxo-groups and metal centres is the only crystallographically imposed symmetry. Oxo-groups are trans in the octahedrally co-ordinated magnesium centre [Mg-O(oxo) 2.036(5), 2.029(5) Å; Mg-O(thf) 2.080(3), 2.1 20(5) Å] and occupy an apical position of square-pyramidally co-ordinated tungsten centres [W-01.744(5), 1.726(4) A; W-CH2 2.162(5)-2.191(4) Å]. Important angles of the metallacycles are: CH2-W-CH2 83.7(2), 85.8(2)°; W-CH2 C(aryl)115.3(4)-121.1(4)°; and torsion angles along the biphenyl axes, 52.9 and 63.1°.
AB - Reaction of the di-Grignard reagent [{Mg(thf)nCl}2{(2-CH2C6H 4)2}], derived from [Mg(anth) (thf)3] (anth = anthracene) and (2-CICH2C6H4)2, with WCI4O in tetrahydrofuran (thf) yields a paramagnetic species, shown by an X-ray diffraction study to be [{W[(2-CH2C6H4)2] 2[graphic omitted]g(thf)4]. Within each molecule the bidentate alkyl ligands have the same chirality, the overall molecular symmetry being approximately 222. A two-fold axis containing the oxo-groups and metal centres is the only crystallographically imposed symmetry. Oxo-groups are trans in the octahedrally co-ordinated magnesium centre [Mg-O(oxo) 2.036(5), 2.029(5) Å; Mg-O(thf) 2.080(3), 2.1 20(5) Å] and occupy an apical position of square-pyramidally co-ordinated tungsten centres [W-01.744(5), 1.726(4) A; W-CH2 2.162(5)-2.191(4) Å]. Important angles of the metallacycles are: CH2-W-CH2 83.7(2), 85.8(2)°; W-CH2 C(aryl)115.3(4)-121.1(4)°; and torsion angles along the biphenyl axes, 52.9 and 63.1°.
UR - http://www.scopus.com/inward/record.url?scp=37049090741&partnerID=8YFLogxK
U2 - 10.1039/DT9860000789
DO - 10.1039/DT9860000789
M3 - Article
AN - SCOPUS:37049090741
SN - 1472-7773
SP - 789
EP - 793
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
IS - 4
ER -