New chemistry of olefin complexes of platinum(ii) unravelled by basic conditions: synthesis and properties of elusive cationic species.

New chemistry of olefin complexes of platinum(ii) unravelled by basic conditions: synthesis and properties of elusive cationic species. Research Abstract Details 

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New chemistry of olefin complexes of platinum(ii) unravelled by basic conditions: synthesis and properties of elusive cationic species. Abstract Text:

The evolution in basic medium ([RO(-)] = 1 M in methanol, R = H or Me) of five-coordinate platinum(ii) compounds, [PtCl(2)(eta(2)-C(2)H(4))(N-N)], , (N-N = N,N,N',N'-tetramethyl-1,2-ethanediamine, ; 2,2'-bipyridyl, ; 1,10-phenanthroline, ) leads to the formation of [PtCl(eta(1)-CH(2)CH(2)-OCH(3))(N-N)], . The analogous compound (N-N = 2,9-dimethyl-1,10-phenanthroline, ) can also be prepared, but not via transformation of the five-coordinate species in basic medium where it is quite stable. can instead be prepared by reaction of with a strongly basic methanol solution of Zeise's anion [PtCl(3)(eta(2)-C(2)H(4))](-), . In such a medium the di-anionic trans-[PtCl(2)(OR)(eta(1)-CH(2)CH(2)-OCH(3))](2-) species () reacts with to form exclusively . Hydrolysis of with acids bearing weakly coordinating anions leads to [PtCl(eta(2)-C(2)H(4))(N-N)](+), , as stable cations; upon the same treatment does not generate , but it reacts with HCl to give in almost quantitative yield. Cationic complexes , , here reported for the first time, were reacted with some nucleophiles and their behaviour compared with that of the already known . In , the metal centre competes with the coordinated ethene for binding to nucleophiles; therefore the acetylacetonate anion can either add to the olefin (affording compounds , ) or to the metal ion replacing the ethene ligand (yielding compounds , ). Under similar conditions, gives exclusively . Secondary amines readily add to ethene in , , affording the addition products , , which undergo a ready cyclization to an azaplatinacyclobutane ring (, ). The remarkable ease of the four-membered ring formation has been related to the high electrophilic character of the metal core in , .

New chemistry of olefin complexes of platinum(ii) unravelled by basic conditions: synthesis and properties of elusive cationic species. Publishing Authors By Initials

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New chemistry of olefin complexes of platinum(ii) unravelled by basic conditions: synthesis and properties of elusive cationic species. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Dalton transactions (Cambridge, England : 2003)

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Page Numbers: 5313-22

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ISSN: 1477-9226

DAY: 21

MONTH: 08

YEAR: 2008

New chemistry of olefin complexes of platinum(ii) unravelled by basic conditions: synthesis and properties of elusive cationic species. Information

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LANGUAGE: eng

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Grant and Affiliation Information for New chemistry of olefin complexes of platinum(ii) unravelled by basic conditions: synthesis and properties of elusive cationic species.

AFFILIATION: Dipartimento Farmaco-Chimico, Università degli Studi di Bari, Via E. Orabona 4, 70125, Bari, Italy. maresca@farmchim.uniba.it.

Country: England

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