期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 2020, 期 42, 页码 4037-4044出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.202000737
关键词
Bis(amidinate); Reductive coupling; Polymers; Reducing agent; Dehydrochlorination
资金
- Australian Research Council
- US Air Force Asian Office of Aerospace Research and Development [FA2386-18-1-0125]
Treating two 2,6-diisopropylphenyl (Dip) substituted, 1,4-phenylene or 1,4-cyclohexylene bridged, bis(amidine)s, viz. C6Hn{[Dip(H)N](DipN=)C}(2)-1,4 (n= 4 (PhAmid(2)H(2)) or 10 (CyAmid(2)H(2))), with groups 1 and 2 alkyl complexes, proceeded via alkane elimination and the formation of the lithium and magnesium bis(amidinate) complexes, [{(THF)(2)Li}(2)(mu-PhAmid(2))], [{(THF)(3)K(mu-PhAmid(2))K}(infinity)], [(Et2O)IMg(mu-PhAmid(2))MgI(OEt2)(2)], and [{(Et2O)(2)IMg}(2)(mu-CyAmid(2))]. The crystal structures of the complexes reveal variable modes of coordination at the metal centre. Two lithium bis(amidinate) compounds have been utilized in salt elimination reactions with group 13 and 14 halides, yielding a series of bis(amidinato) aluminum(III), silicon(IV), germanium(II) and tin(II) halide complexes, viz. [(I2Al)(2)(mu-PhAmid(2))], [(X3Si)(2)(mu-PhAmid(2))] (X = Cl, Br or Cl/H), [(ClM)(2)(mu-PhAmid(2))] (M = Ge or Sn), and [(ClGe)(2)(mu-CyAmid(2))]. Attempts to reduce the bis(amidinato) metal(loid) halide complexes with a series of s-block metal reducing agents have been carried out, with the aim of obtaining dinuclear or polymeric bis(amidinato) metal(I) systems. However, these reductions typically led to intractable mixtures of products. In other attempted reductions, treating [(Cl2HSi)(2)(mu-PhAmid(2))] with two N-heterocyclic carbenes (NHCs), :C{(RNCMe)(2)} (R = Me (TMC) or Pr-i(IPrIMe)) led to single dehydrochlorination reactions, affording the cyclohexa-2,5-diene-1,4-diylidene bridged bis(diamide) silicon(IV) complexes, [{(NHC)Cl2Si}{mu-(DipN)(2)C=(C6H4)=C(NDip)(2)}{SiHCl(NHC)}] (NHC = TMC or IPrIMe), in which the bis(amidinate) ligand has been transformed into a tetra(amide).
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