TY - JOUR
T1 - Axially asymmetric metal alkyls
T2 - VIII. The ruthenium metallacycle [Ru{(2-CH2C6H4)2}(PPhMe2)3 and o-metallated [ 6H4(Me)2}X(PPhMe2)3] (X Cl, Br)
AU - Chappell, S. David
AU - Engelhardt, Lutz M.
AU - White, Allan H.
AU - Raston, Colin L.
PY - 1993/12/14
Y1 - 1993/12/14
N2 - Reaction of cis-[RuCl2(PPhMe2)4] with {(TMEDA)Li}2{(2-CH2C6H4) 2} yields the thermally unstable metallacycloheptadiene, [Ru{(2-CH2C6H4)2}(PPhMe 2)3] (1), which in the solid has a distorted square pyramidal structure with the two ligating carbon atoms in the basal plane (mean RuC 2.14 Å), although there is an agostic-H interaction to an o-hydrogen of a phenyl group (2.80 Å) trans to the apical P-centre, and a secondary interaction to one of the β-carbon atoms of the metallacycle (2.63(4) Å) effectively saturating the metal centre. Treatment of trans-[RuCl2(PPhMe2)4] with 2-[(THF) nClMgCH2]C6H4C6H 4Me-2′ in refluxing THF yields the o-metallated product, [Ru{PC6H4(Me) 2}Cl(PPhMe2)3] (2) which has been characterized by NMR spectroscopy, and by an X-ray structure determination for the corresponding bromide, [Ru{PC6H5(Me)2}Br(PPhMe2) 3] (2′).
AB - Reaction of cis-[RuCl2(PPhMe2)4] with {(TMEDA)Li}2{(2-CH2C6H4) 2} yields the thermally unstable metallacycloheptadiene, [Ru{(2-CH2C6H4)2}(PPhMe 2)3] (1), which in the solid has a distorted square pyramidal structure with the two ligating carbon atoms in the basal plane (mean RuC 2.14 Å), although there is an agostic-H interaction to an o-hydrogen of a phenyl group (2.80 Å) trans to the apical P-centre, and a secondary interaction to one of the β-carbon atoms of the metallacycle (2.63(4) Å) effectively saturating the metal centre. Treatment of trans-[RuCl2(PPhMe2)4] with 2-[(THF) nClMgCH2]C6H4C6H 4Me-2′ in refluxing THF yields the o-metallated product, [Ru{PC6H4(Me) 2}Cl(PPhMe2)3] (2) which has been characterized by NMR spectroscopy, and by an X-ray structure determination for the corresponding bromide, [Ru{PC6H5(Me)2}Br(PPhMe2) 3] (2′).
UR - http://www.scopus.com/inward/record.url?scp=0011047934&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(93)83370-B
DO - 10.1016/0022-328X(93)83370-B
M3 - Article
AN - SCOPUS:0011047934
SN - 0022-328X
VL - 462
SP - 295
EP - 300
JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY
JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY
IS - 1-2
ER -