- Platinum(II) complexes containing unsaturated ligands. Nucleophilic substitution versus nucleophilic attack to ligand: A stereochemistry driven outcome
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The reactivity of mixed complexes [PtCl2(L)(L′)] (L = MeCN, EtCN, CO), L′ = PPh3; L = η2-C 2H4, CO; L′ = MeCN, EtCN) towards diethylamine has been investigated. The processes are chemo- (substitution versus addition) and stereo-selective in dependence of the stereochemistry of the precursor. The structures of [SP4-4]-[PtCl(CONEt2)(NHEt2)(PPh 3)], [SP4-4]-1, trans-[PtCl2(NHEt2)(PPh 3)], trans-2, and cis-[PtCl2{(E-)HNC(NEt 2)Me}(PPh3)], cis-3a, are reported.
- Dell'Amico, Daniela Belli,Broglia, Claudio,Labella, Luca,Marchetti, Fabio,Mendola, Daniele,Samaritani, Simona
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p. 181 - 188
(2013/07/05)
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- Transfer of Cyclopentadienyl Groups between Platinum Atoms
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Replacement of a chloride ion of cis- (PR3 = tertiary phosphine) by a cyclopentadienyl group from Tl(C5H5) or Hg(C5H5)2 results exclusively in the isomers of with C5H5 trans to PR3.The second chloride can be replaced when excess Tl(C5H5) is used.The ?-bonded cyclopentadienyl groups of either mono- or di-substituted compounds can readily exchange in solution with a chloride of cis- again producing exclusively the same isomers of .The cyclopentadienyl groups do not transfer as fast as chloride ions between the same species, but do so considerably faster than any accompanying CO scrambling processes.Cyclopentadienyl groups from the ?-bonded complexes, and from 5-C5H5)(PR3)2>Cl, can also be readily transferred to mercury when treated with HgCl2.
- Cross, Ronald J.,McLennan, Alistair
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p. 359 - 362
(2007/10/02)
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- Reactivity of platinum diolefin complexes. Roles of trans influence and chelate effect
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The complex [PtCl2(cod)] (cod = 1,5-cyclooctadiene) reacts with CO and tertiary phosphine to produce cis-[PtCl2(CO)L] (L = PEt3, P-n-Bu3, PMePh2, PPh3, P(C6H4F-p)
- Anderson,Clark,Davies
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p. 1636 - 1639
(2008/10/08)
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- Preparation of the Complexes trans- and their Isomerisation to cis Isomers
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Treatment of halide-bridged dimers 2> (X is halide; L is tertiary phosphine or arsine) by carbon monoxide gives solutions of the trans isomers of , some of which can be isolated.These compounds readily lose CO and isomerise to cis deriv
- Anderson, Gordon K.,Cross, Ronald J.
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p. 1988 - 1991
(2007/10/02)
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- Carbonyl Insertion at : The Effects of varying the Anionic Ligand X and the Neutral Ligand L
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From the reaction of HgPh2 with cis-, the benzoyl complexes can be isolated when L = PEt3, PMe2Ph, PMePh2, PPh3, or P(C6H11)3, but when L = P(C6H4Me-o)3, AsMePh2, or AsPh3 only the complexes are formed.Metathetical replacements of the chloride ions in lead to the corresponding bromide or iodid complexes.Low temperature n.m.r. studies show that the reaction between HgPh2 and cis- gives first the carbonyl derivative , from which CO insertion proceeds.The equilibrium positions in solution between L> (each with Ph trans to L) and the binuclear benzoyl complexes are reported.The effect of X on the equilibrium position depends on the bridging ability of that group in the benzoyl dimers, stronger bridges favouring the insertion product.The neutral ligans L exert an effect by both electronic and steric factors.The magnitude of the trans influence of L directly affects the tendency of the trans phenyl group to migrate to CO, unless a critical size of L is exceeded.In these cases, the steric bulk of L favours the mononuclear carbonyl derivative.
- Anderson, Gordon K.,Cross, Ronald J.
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p. 712 - 715
(2007/10/02)
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