TY - JOUR
T1 - Preparation, characterization, and theoretical analysis of group 14 element(I) dimers
T2 - A case study of magnesium(I) compounds as reducing agents in inorganic synthesis
AU - Jones, Cameron
AU - Bonyhady, Simon J.
AU - Holzmann, Nicole
AU - Frenking, Gernot
AU - Stasch, Andreas
PY - 2011/12/19
Y1 - 2011/12/19
N2 - A synthetic route to the new amidine (DipNH)(DipN)- C(C6H 4But-4) (ButisoH; Dip = C6H3Pr i 2-2,6) has been developed. Its deprotonation with either LiBun or KN(SiMe3)2 yields the amidinate complexes [M(Butiso)] (M = Li or K). Their reactions with group 14 element halides/pseudohalides afford the heteroleptic group 14 complexes [(Butiso)SiCl3], [(Butiso)ECl] (E = Ge or Sn), and [{(Butiso)- Pb(μ-O 3SCF3)(THF)}∞], all of which have been crystallographically characterized. In addition, the synthesis and spectroscopic characterization of the homoleptic complex [Pb(Butiso)2] is reported. Reductions of the heteroleptic complexes with a soluble magnesium(I) dimer, [{(MesNacnac)Mg}2] (MesNacnac = [(MesNCMe) 2CH]̄; Mes = mesityl), have given moderate-to-high yields of the group 14 element(I) dimers [{(Butiso)E}2] (E = Si, Ge, or Sn), the X-ray crystallographic studies of which reveal trans-bent structures. The corresponding lead(I) complex could not be prepared. Comprehensive spectroscopic and theoretical analyses of [{(Butiso)E}2] have allowed their properties to be compared. All complexes possess E-E single bonds and can be considered as intramolecularly base-stabilized examples of ditetrelynes, REER. Taken as a whole, this study highlights the synthetic utility of soluble and easy to prepare magnesium(I) dimers as valuable alternatives to the harsh, and often insoluble, alkali-metal reducing agents that are currently widely employed in the synthesis of low-oxidation-state organometallic/inorganic complexes.
AB - A synthetic route to the new amidine (DipNH)(DipN)- C(C6H 4But-4) (ButisoH; Dip = C6H3Pr i 2-2,6) has been developed. Its deprotonation with either LiBun or KN(SiMe3)2 yields the amidinate complexes [M(Butiso)] (M = Li or K). Their reactions with group 14 element halides/pseudohalides afford the heteroleptic group 14 complexes [(Butiso)SiCl3], [(Butiso)ECl] (E = Ge or Sn), and [{(Butiso)- Pb(μ-O 3SCF3)(THF)}∞], all of which have been crystallographically characterized. In addition, the synthesis and spectroscopic characterization of the homoleptic complex [Pb(Butiso)2] is reported. Reductions of the heteroleptic complexes with a soluble magnesium(I) dimer, [{(MesNacnac)Mg}2] (MesNacnac = [(MesNCMe) 2CH]̄; Mes = mesityl), have given moderate-to-high yields of the group 14 element(I) dimers [{(Butiso)E}2] (E = Si, Ge, or Sn), the X-ray crystallographic studies of which reveal trans-bent structures. The corresponding lead(I) complex could not be prepared. Comprehensive spectroscopic and theoretical analyses of [{(Butiso)E}2] have allowed their properties to be compared. All complexes possess E-E single bonds and can be considered as intramolecularly base-stabilized examples of ditetrelynes, REER. Taken as a whole, this study highlights the synthetic utility of soluble and easy to prepare magnesium(I) dimers as valuable alternatives to the harsh, and often insoluble, alkali-metal reducing agents that are currently widely employed in the synthesis of low-oxidation-state organometallic/inorganic complexes.
UR - http://www.scopus.com/inward/record.url?scp=79959896712&partnerID=8YFLogxK
U2 - 10.1021/ic200682p
DO - 10.1021/ic200682p
M3 - 文章
AN - SCOPUS:79959896712
SN - 0020-1669
VL - 50
SP - 12315
EP - 12325
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 24
ER -