TY - JOUR
T1 - Synthesis and structural characterisation of group 10 metal(ii) gallyl complexes
T2 - Analogies with platinum diboration catalysts?
AU - Jones, Cameron
AU - Mills, David P.
AU - Rose, Richard P.
AU - Stasch, Andreas
PY - 2008/7/3
Y1 - 2008/7/3
N2 - Reactions of the anionic gallium(i) heterocycle, [:Ga([N(Ar)C(H)]2)]− (Ar = C6H3Pri2-2,6), 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)]2))(PEt3)2] (M = Ni or Pd) and cis-[PtCl(Ga([N(Ar)C(H)]2))(L)] (L = R2PCH2CH2PR2, R = Ph (dppe) or cyclohexyl (dcpe)), or bis(gallyl) complexes, trans-[M(Ga([N(Ar)C(H)]2))2(PEt3)2] (M = Ni, Pd or Pt), cis-[Pt(Ga([N(Ar)C(H)]2))2(PEt3)2], cis-[M(Ga([N(Ar)C(H)]2))2(L)] (M = Ni, Pd or Pt; L = dppe, Ph2CH2PPh2 (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− > PR3 ∼ [:Ga([N(Ar)C(H)]2)]− > Cl−. Comparisons between the reactivity of one complex, [Pt(Ga([N(Ar)C(H)]2))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, ButCP, 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)]2))(Ga(PC(But)C(H)[N(Ar)]C(H)N(Ar)))(dppe)]. An investigation into the mechanism of this insertion reaction has been undertaken.
AB - Reactions of the anionic gallium(i) heterocycle, [:Ga([N(Ar)C(H)]2)]− (Ar = C6H3Pri2-2,6), 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)]2))(PEt3)2] (M = Ni or Pd) and cis-[PtCl(Ga([N(Ar)C(H)]2))(L)] (L = R2PCH2CH2PR2, R = Ph (dppe) or cyclohexyl (dcpe)), or bis(gallyl) complexes, trans-[M(Ga([N(Ar)C(H)]2))2(PEt3)2] (M = Ni, Pd or Pt), cis-[Pt(Ga([N(Ar)C(H)]2))2(PEt3)2], cis-[M(Ga([N(Ar)C(H)]2))2(L)] (M = Ni, Pd or Pt; L = dppe, Ph2CH2PPh2 (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− > PR3 ∼ [:Ga([N(Ar)C(H)]2)]− > Cl−. Comparisons between the reactivity of one complex, [Pt(Ga([N(Ar)C(H)]2))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, ButCP, 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)]2))(Ga(PC(But)C(H)[N(Ar)]C(H)N(Ar)))(dppe)]. An investigation into the mechanism of this insertion reaction has been undertaken.
UR - http://www.scopus.com/inward/record.url?scp=85034329665&partnerID=8YFLogxK
U2 - 10.1039/b715895e
DO - 10.1039/b715895e
M3 - Article
SN - 1477-9226
SP - 4395
EP - 4408
JO - Dalton Transactions
JF - Dalton Transactions
IS - 33
ER -