Synthesis and reactivity of platinacycloalkanes

Sivaramakrishna, Akella; Makhubela, Banothile C.E.; Moss, John R.; Smith, Gregory S.

doi:10.1016/j.jorganchem.2010.04.011

Cited by 11 publications

(8 citation statements)

References 61 publications

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“…The RCM reaction of 16 with 2 mol diphenylacetylene ( 28 ) in the presence of Grubbs’ catalyst yielded a mixture of products including platinacyclononene as a major species and an unexpected product via insertion of diphenylacetylene into the metallacycle. Hydrogenation of this mixture gave 29 and 30 and these products yielded 1‐octene, 1,7‐octadiene and n ‐octane (observed by GC‐MS), as well as 31 on thermal decomposition (Scheme ).…”

Section: Reactivitymentioning

confidence: 99%

“…Several factors that can affect the RCM reaction includes high concentration of precursors in the reaction resulted in the formation of dimers ( 24 ) and polymers ( 25 ) (Scheme ) . The high‐temperature conditions favor complete decomposition.…”

Section: Reactivitymentioning

confidence: 99%

“…Reaction of 16 with 1,7‐octadiene ( 26 ) in the presence of 5 mol% Grubbs’ catalyst resulted in the formation of 5,11‐platinacyclodiene, which on hydrogenation in the presence Pd catalyst yielded a 15‐membered platinacycle ( 27 ) (equation ).…”

Section: Reactivitymentioning

confidence: 99%

“…The chelating effect of diphosphines reduces the amount of decomposition of 1‐alkenyl compounds even at high temperatures. The PPh 3 ‐ and P t Bu 3 ‐containing metal‐alkenyl complexes, however, decompose rapidly above 80°C and hence the isomerization could not be detected with these ligands . Hence, platinum(II)‐alkenyl complexes can be proposed as model intermediates in catalytic reactions .…”

Section: Reactivitymentioning

confidence: 99%

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Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Sravani

Venkatesh

Vijayakrishna

et al. 2014

Applied Organom Chemis

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Intermediates for many catalysis reactions reported in the literature are metal‐alkyl and metal‐alkenyl, including metallacycloalkane species. Synthesis and reactions of metal‐alkyl, alkenyl and metallacyle complexes have shown a great deal of development during the past few decades. This review summarizes the significant contributions reported on metal‐alkenyl compounds, specifically those containing at least a carbon chain with pendant alkene group [M―CH2CH2CHCH2]. Although metal‐alkenyl complexes are stable with strong chelating diphosphines and with a decrease in the ligand donor strength, the complexes can decompose without any ambiguity. For example, platinum‐dialkenyl complexes react readily via β‐hydrogen elimination and reductive elimination promoted by the nature of the ligand, solvent and length of carbon chains. These complexes can also undergo intramolecular irreversible isomerization and this leads to the selective catalytic isomerization of 1‐alkenes to 2‐alkenes in the presence of platinum‐dialkenyl complexes as catalysts. Perhaps the most striking manifestations of flexibility are the facile and complete intramolecular and intermolecular alkene metathesis to yield the corresponding metallacycloalkenes in the presence of Grubbs’ catalysts. The diverse chemical reactivity of these complexes demonstrates both the scope and complexity of metal‐alkenyl chemistry depending on the nature of ligand and metal. Copyright © 2014 John Wiley & Sons, Ltd.

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Section: Reactivitymentioning

confidence: 99%

Section: Reactivitymentioning

confidence: 99%

Section: Reactivitymentioning

confidence: 99%

Section: Reactivitymentioning

confidence: 99%

See 2 more Smart Citations

Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Sravani

Venkatesh

Vijayakrishna

et al. 2014

Applied Organom Chemis

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“…These signals are accompanied by platinum satellites with coupling constants in the range 1 J PPt = 1843-2066 Hz, similar to other platinacycloalkane phosphine complexes. [50][51][52][53][54] In the IR spectra of the platinacycles, the imine stretching band is observed in the region 1630-1635 cm −1 , a slightly lower frequency compared to the free ligands where the imine absorption band is seen between 1634-1636 cm −1 . This confirms coordination of the imine nitrogen to platinum.…”

Section: Preparation Of Platinacyclopentanes 2a-2f and Platinacyclohementioning

confidence: 99%

Platinacycloalkane complexes containing [P,N] bidentate ligands: synthesis and decomposition studies

et al. 2014

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A new series of platinacyclopentanes (2a-2f) and platinacycloheptanes (3a-3f) of the type [Pt(N^P)(CH2)n] (n = 4, 6) were obtained by the reaction of [Pt(COD)(CH2)n] with the appropriate iminophosphine ligand (1a-1f). These complexes were characterised using a variety of spectroscopic and analytical techniques. X-ray structure analysis of complex 2a revealed a slightly distorted square planar geometry around platinum as a consequence of the ring strain imposed by the [P,N] chelate ring formed and the metallocycloalkane. Thermal decomposition analyses of the platinacycloalkanes revealed that the platinacyclopentanes are markedly stable, with the decomposition reaction requiring temperatures higher than 100 °C to occur. The major products obtained from the thermal decomposition reactions were 1-butene (for platinacyclopentanes) and 1-hexene (for platinacycloheptanes).

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The chemistry of the carbon–transition metal double and triple bond: Annual survey covering the year 2010

Herndon

2012

Coordination Chemistry Reviews

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Synthesis and reactivity of platinacycloalkanes

Cited by 11 publications

References 61 publications

Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Platinacycloalkane complexes containing [P,N] bidentate ligands: synthesis and decomposition studies

The chemistry of the carbon–transition metal double and triple bond: Annual survey covering the year 2010

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