TY - JOUR
T1 - Syntheses and structures of highly hindered N-functionalised alkyl and amido group 12 complexes MR2 (M=Zn, Cd, and Hg), [MRCl]2 (M=Zn and Hg)
AU - van den Ancker, Tania R.
AU - Engelhardt, Lutz M.
AU - Henderson, Mark J.
AU - Jacobsen, Geraldine E.
AU - Raston, Colin L.
AU - Skelton, Brian W.
AU - White, Allan H.
PY - 2004/6/1
Y1 - 2004/6/1
N2 - The reaction of MCl2 (M=Zn, Cd and Hg) with Li(2-(C(SiMe3)2)(6-Me-C5 H3N)), [Li(MeR)], affords mononuclear metal(II) alkyls. These, in the solid state, show intramolecular M-N interactions in their four-membered chelate rings, which progressively weaken down the series, the C-M-C angles becoming more open (〈M-N〉= 2.30(2), 2.52(2), 2.913(4) Å, C-M-C=160.7(2), 168.5(2), 180(-)°). Alkylmercury chloride complexes have been prepared by the reaction of HgCl2 with [Li(MeR)], Li(2-(C(SiMe3)2) (C5H4N)), [Li(HR)], or Li(2-(NSiMe3) (6-Me-C5H3N)), [Li(mpsa)], or from the redistribution reaction of the dialkyl (or amido) mercury complex with HgCl2. The alkylmercury chloride complexes are dimeric or polymeric in nature with near-linear 2-coordination; (Hg-Cl=2.329(5), 2.318(4), 2.272(8) Å, Cl-Hg-C(N)=175.0(4), 174.7(4), 175.6(5)°). Cd(2-(CH(SiMe3)) (6-Me-C5H3N))2(tmen), prepared from the reaction of Li(2-(CH(SiMe3)) (6-Me-C5H3N)) and CdCl2 in the presence of tmen, has also been structurally authenticated as the rac isomer with the ipso protons directed towards the tmen.
AB - The reaction of MCl2 (M=Zn, Cd and Hg) with Li(2-(C(SiMe3)2)(6-Me-C5 H3N)), [Li(MeR)], affords mononuclear metal(II) alkyls. These, in the solid state, show intramolecular M-N interactions in their four-membered chelate rings, which progressively weaken down the series, the C-M-C angles becoming more open (〈M-N〉= 2.30(2), 2.52(2), 2.913(4) Å, C-M-C=160.7(2), 168.5(2), 180(-)°). Alkylmercury chloride complexes have been prepared by the reaction of HgCl2 with [Li(MeR)], Li(2-(C(SiMe3)2) (C5H4N)), [Li(HR)], or Li(2-(NSiMe3) (6-Me-C5H3N)), [Li(mpsa)], or from the redistribution reaction of the dialkyl (or amido) mercury complex with HgCl2. The alkylmercury chloride complexes are dimeric or polymeric in nature with near-linear 2-coordination; (Hg-Cl=2.329(5), 2.318(4), 2.272(8) Å, Cl-Hg-C(N)=175.0(4), 174.7(4), 175.6(5)°). Cd(2-(CH(SiMe3)) (6-Me-C5H3N))2(tmen), prepared from the reaction of Li(2-(CH(SiMe3)) (6-Me-C5H3N)) and CdCl2 in the presence of tmen, has also been structurally authenticated as the rac isomer with the ipso protons directed towards the tmen.
KW - Group 12
KW - Intramolecular
KW - N-functionalised alkyl and amido
UR - http://www.scopus.com/inward/record.url?scp=2342625228&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2004.03.023
DO - 10.1016/j.jorganchem.2004.03.023
M3 - Article
AN - SCOPUS:2342625228
SN - 0022-328X
VL - 689
SP - 1991
EP - 1999
JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY
JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY
IS - 11
ER -