Alkoxycarbene complexes of nickel(II)

Alkynylnickel complexes trans-C₆Cl₅Ni(PPhMe₂)₂CCR (IIIa, R  H; IIIb, R  Me; IIIc, R  Et; IIId, R  CH₂OH; IIIe, R  CH₂CH₂OH; IIIf, R  Ph; IIIg, R  C₆H₄OMe-p) have been prepared from trans-[C₆Cl₅Ni-(PPhMe₂)₂L]ClO₄ and monosubstituted acetylenes in the presence of triethylamine, and their reactions with alcohols in the presence of perchloric acid were studied. Complexes IIIa and IIIe afforded alkoxycarbene complexes trans-[C₆Cl₅Ni-(PPhMe₂)₂{C(OR′)Me}]ClO₄ (IVa, R′  Me; IVb, R′  Et; IVc, R′  n-Pr) or trans-C₆Cl₅Ni(PPhMe₂)₂{$\text{C(CH}{}_2\text{)}{}_3\text{O}$}]ClO₄(IVd), respectively, but IIIb either decomposed or afforded trans-C₆Cl₅Ni(PPhMe₂)₂CHC(OMe)Me, depending on the amount of acid used. Treatment of IVaIVd with amines resulted in deprotonation to give α-alkoxyvinyl complexes, trans-C₆Cl₅Ni(PPhMe₂)₂C(OR′)CH₂ (VIaVIc) or trans-C₆Cl₅Ni(PPhMe₂)₂$\text{CCHCH}{}_2\text{CH}{}_2\text{O}$ (VId), the reaction being reversible. A ¹H NMR study indicated: (i) that the carbene methyl and the vinyl protons IV or VI are D-exchangeable by MeOD without catalyst; (ii) that the basicity of VIa is comparable to those of amines; (iii) that the carbene complexes IVaIVc have two isomers due to hindered rotation about the C(carbene)O bond in solution, IVb existing in the Z-form in the solid state; (iv) that the rotationalbarriers (°G^≠) about the C(carbene)O bond in IVb and the NiC-(carbene) bond in IVd are 20 (or more) and 11.7 kcal/mol, respectively. These results are explained in term of double bond character of the carbene carbon and its surrounding atoms.