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The generation of cationic palladium complexes that contain halogenated alkyl ligands (RX) and their reactivity with vinyl chloride, ethylene, and CO are described. {(nHex)HC-(mim)2}Pd(CHCl2)Cl (1; nHex = n-hexyl, mim = N-methylimidazol-2-yl) reacts with 0.5 equiv of [Li(Et2O)2.8][B(C6F5)4] to form [{{(nHex)HC(mim)2}Pd(CHCl2)}2(mu- Cl)][B(C6F5)4] as a 1:1 mixture of diastereomer (3a,b). 3a,b do not react with vinyl chloride. The reaction of 1 with 1 equiv of [Li(Et2O)2.8][B(C6F5)4] in the presence of ethylene or CO yields [{(nHex)HC-(mim)2}Pd(CHCl2)(L)][B(C6 F5)4] adducts (L = ethylene (4), CO (5)). The reaction of (dppp)-Pd(nC3F7)Me (7; dppp = 1,3-bis(diphenylphosphino)propane) with [HNMePh2][B(C6F5)4] yields [(dppp)Pd(nC3F7)(NMePh2)][B (C6F5)4] (8). 8 does not react with vinyl chloride or ethylene but does react with CO to form [(dppp)Pd(nC3F7)(CO)][B(C6 F5)4] (9). 4, 5, and 9 do not undergo insertion under mild conditions. The reaction of (tBu2bipy)Pd(CH2Cl)Cl (10; tBu2bipy = 4,4?-di-tert-butyl-2,2?-bipyridine) with 0.5 equiv of [Li(Et2O)2.8][B(C6F5)4] yields [{(tBu2bipy)Pd-(CH2Cl)}2(mu-Cl)][B (C6F5)4] (11). In the presence of one equiv of [Li(Et2O)2.8][B(C6F5)4], 11 reacts with vinyl chloride by net 1,2-insertion and beta-Cl elimination to generate Pd-Cl+ species and allyl chloride and with CO at -78C to form [(tBu2bipy)Pd(CH2Cl)(CO)] [B(C6F5)4] (12). At 20C, 12 undergoes slow CO insertion followed by beta-Cl elimination to generate Pd-Cl+ species and ketene. The reaction of (alpha-diimine)Pd(CH2Cl)Cl (13; alpha-diimine = (2,6-iPr2-C6H3)N=CMeCMe= N(2,6-iPr2-C6H3)) with 1 equiv of [Li(Et2O)2.8][B(C6F5)4] in the presence of vinyl chloride yields Pd-Cl+ species and allyl chloride, most likely via net 1,2-insertion and beta-Cl elimination of a (alpha-diimine)Pd(CH2Cl)(CH2=CHCl)+ intermediate. In general, L2Pd(RX)(substrate)+ species undergo slower insertion than non-halogen-substituted L2Pd(R)-(substrate)+ analogues.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method