Mechanistic aspects of palladium-catalyzed insertion copolymerizations of ethylene and α-olefins with methyl acrylate to give high molar mass polymers are described. Complexes [(N∧N)Pd(CH2)3C(O)OMe]BAr‘4 (2) or [(N∧N)Pd(CH3)(L)]BAr‘4 (1:  L = OEt2; 3:  L ⋮ NCMe; 4:  L ⋮ NCAr‘) (N∧N ≡ ArNC(R)−C(R)NAr, e.g., Ar ⋮ 2,6-C6H3(i-Pr)2, R ⋮ H (a), Me (b); Ar‘ ⋮ 3,5-C6H3(CF3)2) with bulky substituted α-diimine ligands were used as catalyst precursors. The copolymers are highly branched, the acrylate comonomer being incorporated predominantly at the ends of branches as −CH2CH2C(O)OMe groups. The effects of reaction conditions and catalyst structure on the copolymerization reaction are rationalized. Low-temperature NMR studies show that migratory insertion in the η2-methyl acrylate (MA) complex [(N∧N)PdMe{H2CCHC(O)OMe}]+ (5) occurs to give initially the 2,1-insertion product [(N∧N)PdCH(CH2CH3)C(O)OMe]+ (6), which rearranges stepwise to yield 2 as the final product upon warming to −20 °C. Activation parameters (ΔH⧧ = ...

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Mechanistic Studies of the Palladium-Catalyzed Copolymerization of Ethylene and α-Olefins with Methyl Acrylate

Synthetic Methods for Compounds Having CF3–S Units on Carbon by Trifluoromethylation, Trifluoromethylthiolation, Triflylation, and Related Reactions

Carbon trifluoromethylation reactions of hydrocarbon derivatives and heteroarenes.

Monofluorination of Organic Compounds: 10 Years of Innovation.

Reactions of Hydrosilanes with Transition-Metal Complexes: Formation of Stable Transition-Metal Silyl Compounds.

Organic reactions involving transition metals III. The palladium(II)-catalysed dimerization of olefinic compounds☆

Metal carbonyl chemistry

Organosilicon chemistry: XI. The stereochemistry of Ir(H)Cl(SiR3)CO(PPh3)2, and the trans-influence of substituted silyl, germyl, and stannyl groups

Organosilicon chemistry : XXX. Homogeneous catalysis by iridium(I) complexes of the reaction between silanes and alcohols or dideuterium☆

The complexes [CoH(X2)L3](X = H or N; L = PPh3) react with silanes, SiR3H, to give the new silylcobalt(III) complexes [CoH2(SiR3)L3][R3= F3, MeF2, or (OEt)3]. The characterization of these complexes and their reactions with N2, H2, HCl, CCl4, and CO are described. With CO the new cobalt(I) silyl [Co(SiF3)(CO)2L2] is formed. The stability of the silyls to loss of SiR3H decreases as the electronegativity of R decreases, which allows the less-stable complexes to participate in catalytic processes. The reaction of SiR3H with D2(R = F, OEt, Et, or Me), of SiH(OEt)3 or Me3Si[OSi(H)Me]nOSiMe3 with EtOH, and of SiH(OEt)3 with hex-1-ene are catalysed by [CoH(X2)L3] or by [CoH2{Si(OEt)3}L3]. The deuteriation reaction provide an easy routr to deuteriosilanes, SiR3D.

Organosilicon chemistry. Part 23. Some silylcobalt(III) complexes and the homogeneous catalysis of deuteriation, hydrosilylation, and O-silylation reactions

Robert N. Haszeldine

Papers

Organic reactions involving transition metals III. The palladium(II)-catalysed dimerization of olefinic compounds☆

Metal carbonyl chemistry

Organosilicon chemistry: XI. The stereochemistry of Ir(H)Cl(SiR3)CO(PPh3)2, and the trans-influence of substituted silyl, germyl, and stannyl groups

Organosilicon chemistry : XXX. Homogeneous catalysis by iridium(I) complexes of the reaction between silanes and alcohols or dideuterium☆

Organosilicon chemistry. Part 23. Some silylcobalt(III) complexes and the homogeneous catalysis of deuteriation, hydrosilylation, and O-silylation reactions