Jones Cameron, Mills David P, Rose Richard P, Stasch Andreas
School of Chemistry, PO Box 23, Monash University, VIC, 3800, Australia.
Dalton Trans. 2008 Sep 7(33):4395-408. doi: 10.1039/b715895e. Epub 2008 Jul 3.
Reactions of the anionic gallium(i) heterocycle, :Ga{N(Ar)C(H)} (Ar = C(6)H(3)Pr(i)(2)-2,6), with a variety of mono- and bidentate phosphine, tmeda and 1,5-cyclooctadiene (COD) complexes of group 10 metal dichlorides are reported. In most cases, salt elimination occurs, affording either mono(gallyl) complexes, trans-[MCl{Ga{N(Ar)C(H)}}(PEt(3))(2)] (M = Ni or Pd) and cis-[PtCl{Ga{N(Ar)C(H)}}(L)] (L = R(2)PCH(2)CH(2)PR(2), R = Ph (dppe) or cyclohexyl (dcpe)), or bis(gallyl) complexes, trans-[M{Ga{N(Ar)C(H)}}(2)(PEt(3))(2)] (M = Ni, Pd or Pt), cis-[Pt{Ga{N(Ar)C(H)}}(2)(PEt(3))(2)], cis-[M{Ga{N(Ar)C(H)}}(2)(L)] (M = Ni, Pd or Pt; L = dppe, Ph(2)CH(2)PPh(2) (dppm), tmeda or COD). The crystallographic and spectroscopic data for the complexes show that the trans-influence of the gallium(i) heterocycle lies in the series, B(OR)(2) > H(-) > PR(3) approximately :Ga{N(Ar)C(H)} > Cl(-). Comparisons between the reactivity of one complex, [Pt{Ga{N(Ar)C(H)}}(2)(dppe)], with that of closely related platinum bis(boryl) complexes indicate that the gallyl complex is not effective for the catalytic or stoichiometric gallylation of alkenes or alkynes. The phosphaalkyne, Bu(t)C[triple bond, length as m-dash]P, does, however, insert into one gallyl ligand of the complex, leading to the novel, crystallographically characterised P,N-gallyl complex, [Pt{Ga{N(Ar)C(H)}}{Ga{PC(Bu(t))C(H)[N(Ar)]C(H)N(Ar)}}(dppe)]. An investigation into the mechanism of this insertion reaction has been undertaken.
报道了阴离子型镓（I）杂环化合物:Ga{N(Ar)C(H)}（Ar = C(6)H(3)Pr(i)(2)-2,6）与多种第10族金属二氯化物的单齿和双齿膦、四甲基乙二胺（tmeda）及1,5-环辛二烯（COD）配合物的反应。在大多数情况下，发生盐消除反应，生成单（镓烯基）配合物，反式-[MCl{Ga{N(Ar)C(H)}}(PEt(3))(2)]（M = Ni或Pd）和顺式-[PtCl{Ga{N(Ar)C(H)}}(L)]（L = R(2)PCH(2)CH(2)PR(2)，R = Ph（dppe）或环己基（dcpe）），或双（镓烯基）配合物，反式-[M{Ga{N(Ar)C(H)}}(2)(PEt(3))(2)]（M = Ni、Pd或Pt），顺式-[Pt{Ga{N(Ar)C(H)}}(2)(PEt(3))(2)]，顺式-[M{Ga{N(Ar)C(H)}}(2)(L)]（M = Ni、Pd或Pt；L = dppe、Ph(2)CH(2)PPh(2)（dppm）、tmeda或COD）。配合物的晶体学和光谱数据表明，镓（I）杂环的反位影响顺序为：B(OR)(2) > H(-) > PR(3) ≈ :Ga{N(Ar)C(H)} > Cl(-)。对一种配合物[Pt{Ga{N(Ar)C(H)}}(2)(dppe)]与密切相关的铂双（硼基）配合物的反应活性进行比较，结果表明镓烯基配合物对烯烃或炔烃的催化或化学计量镓化反应无效。然而，膦炔Bu(t)C≡P可插入该配合物的一个镓烯基配体中，生成新型的、经晶体学表征的P,N-镓烯基配合物[Pt{Ga{N(Ar)C(H)}}{Ga{PC(Bu(t))C(H)[N(Ar)]C(H)N(Ar)}}(dppe)]。已对该插入反应的机理进行了研究。
