Complexes of the platinum metals containing weak donor ligands

Davies, Julian A.; Hartley, F. R.

doi:10.1021/cr00041a004

Cited by 203 publications

(68 citation statements)

References 34 publications

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“…[5] The chemistry of transition metal complexes with chelating ligands containing mixed functionalities is enjoying an increase in popularity, as the different features associated with each donor atom give unique reactivity to their metal complexes. [6][7][8] Hemilabile ligands, which are a class of chelating ligands, have the ability to place two or more donor atoms with very different electronic properties close to the metal atom ( Figure 1). The relevance of these ligands is increasing in coordination and organometallic chemistry, since they can reversibly create and/or occupy a vacant coordination site at the metal, with consequent stabilisation of reactive intermediates or enhancement of reactivity in catalytic reactions.…”

Section: Introductionmentioning

confidence: 99%

Ruthenium Catalyst with a Chelating Pyridinyl‐Alcoholato Ligand for Application in Linear Alkene Metathesis

Jordaan¹,

Vosloo²

2007

Adv Synth Catal

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The catalytic activity of ruthenium alkylidene complexes [RuCl(L), bearing a chelating pyridinyl-alcoholate ligand, was investigated for the metathesis of 1-octene in the absence of a solvent. Both systems were active for the metathesis of 1-octene yielding trans-7-tetradecene and ethene as the primary metathesis products. Although the activity of both systems increased with an increase in reaction temperature, the activity ofstarted to decrease at temperatures above 70 8C, with a simultaneous exponential increase in the secondary metathesis products due to double-bond isomerisation of the substrate. Although the initiation rates for these systems are slower compared to Grubbs 1 and Grubbs 2 for the metathesis of 1-octene at 60 8C, they have a higher activity and longer lifetime.

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Section: Introductionmentioning

confidence: 99%

Ruthenium Catalyst with a Chelating Pyridinyl‐Alcoholato Ligand for Application in Linear Alkene Metathesis

Jordaan¹,

Vosloo²

2007

Adv Synth Catal

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“…To favor this kind of ligand replacement processes, it is highly desirable that at least one of the ligands in the metal coordination sphere has a reasonable lability. [32] Water and organonitrile ligands [33] are class a ligands that usually exhibit labile behavior when bound to Pt II or Pt IV centers-both considered to be class b metals. [32] Compound 2 dissolved in Me 2 CO reacts with Ag + salts of weakly coordinating anions, such as (SO 3 Table 1).…”

Section: Ja C H T U N G T R E N N U N Gmentioning

confidence: 99%

“…[32] Water and organonitrile ligands [33] are class a ligands that usually exhibit labile behavior when bound to Pt II or Pt IV centers-both considered to be class b metals. [32] Compound 2 dissolved in Me 2 CO reacts with Ag + salts of weakly coordinating anions, such as (SO 3 Table 1). The overall pattern is similar to that observed for compound 2 with the quartet now appear- + is the counterion in all cases).…”

Section: Ja C H T U N G T R E N N U N Gmentioning

confidence: 99%

Highly Trifluoromethylated Platinum Compounds

Martínez-Salvador

Forniés

Martín

et al. 2011

Chemistry A European J

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The homoleptic, square‐planar organoplatinum(II) compound [NBu4]2[Pt(CF3)4] (1) undergoes oxidative addition of CF3I under mild conditions to give rise to the octahedral organoplatinum(IV) complex [NBu4]2[Pt(CF3)5I] (2). This highly trifluoromethylated species reacts with Ag+ salts of weakly coordinating anions in Me2CO under a wet‐air stream to afford the aquo derivative [NBu4][Pt(CF3)5(OH2)] (4) in around 75 % yield. When the reaction of 2 with the same Ag+ salts is carried out in MeCN, the solvento compound [NBu4][Pt(CF3)5(NCMe)] (5) is obtained in around 80 % yield. The aquo ligand in 4 as well as the MeCN ligand in 5 are labile and can be cleanly replaced by neutral and anionic ligands to furnish a series of pentakis(trifluoromethyl)platinate(IV) compounds with formulae [NBu4][Pt(CF3)5(L)] (L=CO (6), pyridine (py; 7), tetrahydrothiophene (tht; 8)) and [NBu4]2[Pt(CF3)5X] (X=Cl (9), Br (10)). The unusual carbonyl–platinum(IV) derivative [NBu4][Pt(CF3)5(CO)] (6) is thermally stable and has a νCO of 2194 cm−1. The crystal structures of 2⋅CH2Cl2, 5, [PPh4][Pt(CF3)5(CO)] (6′), and 7 have been established by X‐ray diffraction methods. Compound 2 has shown itself to be a convenient entry to the chemistry of highly trifluoromethylated platinum compounds. To the best of our knowledge, compounds 2 and 4–10 are the organoelement compounds with the highest CF3 content to have been isolated and adequately characterized to date.

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“…According to the HSAB concept (hard and soft acid and base), 48 oxygen is a hard Lewis base (electron donor) existing in a large number of organic molecules, such as alcohols, ethers, carbonyls (ketones and aldehydes), carboxylic acid and their derivatives, and many others. Consequently, oxygen is expected to form stable complexes with hard Lewis acids.…”

Section: Ethers-lewis Base Properties Oxygen Functionalities and Hardmentioning

confidence: 99%

Chiral recognition of ethers by NMR spectroscopy

Duddeck

Gómez

2008

Chirality

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Enantiomers of chiral ethers and acetals are notoriously difficult to differentiate because their reactivity is low and they are poor donors to any Lewis acid or metal ion. As an exception, epoxides are somewhat better donors. This review describes the properties of ethers, explains NMR methods for their chiral recognition and describes successful examples of ether differentiation. The majority of literature reports deals with chiral lanthanide shift reagents and dirhodium tetracarboxylate complexes, which were used as enantiopure auxiliaries to create diastereomeric adducts with dispersed (1)H and (13)C NMR signals. The various methods are compared as to which is best suited for which purpose.

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Complexes of the platinum metals containing weak donor ligands

Cited by 203 publications

References 34 publications

Ruthenium Catalyst with a Chelating Pyridinyl‐Alcoholato Ligand for Application in Linear Alkene Metathesis

Ruthenium Catalyst with a Chelating Pyridinyl‐Alcoholato Ligand for Application in Linear Alkene Metathesis

Highly Trifluoromethylated Platinum Compounds

Chiral recognition of ethers by NMR spectroscopy

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