Terminal and bridging bonding modes of the acetophenone enolate to palladium(II): the structural evidence and the insertion of isocyanides

Veya, Patrick; Floriani, Carlo; Chiesi‐Villa, Angiola; Rizzoli, Corrado

doi:10.1021/om00036a033

Cited by 77 publications

(83 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The latter results in approximate planarity (within 0.042(6) Å) of Pd-O C(Me)CH 2 -subunit. The same feature was observed in some other binuclear palladium enolate complexes [6,11]. In crystal, hydroxyl atom H1 is involved in intermolecular hydrogen bond with oxygen atom O1 of the solvent acetone molecule (d(O41…O1) = 2.67(1) Å, ∠(O41-H1…O1) = 161.6°).…”

supporting

confidence: 73%

“…The Pd1-C41 bond length (2.159(10) Å) is somewhat longer than the Pd1-C42 and Pd1-C43 distances (2.067(11) and 2.099(10) Å). The dihedral angle between the η 3 -allyl group and the square planar coordination environment of Pd1 atom is 114.5(8)°while C42-C41-C43 angle is 114(1)°.…”

mentioning

confidence: 82%

“…2). Taking into account a great difference in Pd-Pd distances for Pd(μ-RCO 2 ) 2 Pd and Pd(μ,k 2 - (12), Pd1-C41 2.159(10), Pd1-C42 2.067 (11), Pd1-C43 2.099(10), Pd1-O21 2.137 (7), Pd1-O11 2.140 (7), Pd2-C33 2.047(10), Pd2-O31A 2.013 (7), Pd2-O22 2.028 (7), Pd2-O12 2.147 (7), C31-O31 1.242 (12), C31-C33 1.463(15), C31-C32 1.508(15), C41-O41 1.347(13), C41-C42 1.391(16), C41-C43 1.426(15); C42-Pd1-C43 69.1(4), C42-Pd1-O21 171.1(4), C43-Pd1-O11 168.8(4), O21-Pd1-O11 88.7(3), C31-O31-Pd2 129.6(7), O31-C31-C33 122.6(10), O31-C31-C32 117.2(10), C33-C31-C32 120.2(10), C31-C33-Pd2 105.7 (7), O41-C41-C42 120.8(10), O41-C41-C43 123.1(10), C42-C41-C43 114.0(10). CH 2 C(O)CH 3 ) 2 Pd fragments (2.964(1) and 4.229(2) Å in complex I) the A structure (Fig.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Transformations of acetone in reactions with carboxylate complexes of palladium

Ефименко

Podobedov

Shishilov

et al. 2011

Inorganic Chemistry Communications

View full text Add to dashboard Cite

supporting

confidence: 73%

mentioning

confidence: 82%

mentioning

confidence: 99%

See 1 more Smart Citation

Transformations of acetone in reactions with carboxylate complexes of palladium

Ефименко

Podobedov

Shishilov

et al. 2011

Inorganic Chemistry Communications

View full text Add to dashboard Cite

“…, respectively [27]. These data strongly suggest that the carbonyl group is coordinated to the Pd-atom, affording the proposed four-membered palladacycle involving a (carbonyl-kO)alkyl-kC moiety (Scheme 3).…”

Section: Scheme 2 Schemementioning

confidence: 74%

“…Alternatively, complex 16 could be a dimer, in analogy with the complex [{cis- [27]. To shed some light on this possibility, we performed PGSE measurements on a mixture containing 13 (ca.…”

Section: Scheme 2 Schemementioning

confidence: 99%

Synthesis, Interionic Structure, and Reactivity toward CO and p‐Methylstyrene of Palladacyclic Compounds Bearing α‐Diimine Ligands

Zuccaccia¹,

Bellachioma²,

Cardaci³

et al. 2006

Helvetica Chimica Acta

View full text Add to dashboard Cite

Dedicated to Professor Giambattista Consiglio on the occasion of his 65th birthday Palladacyclic compounds [Pd(C 6 [X] complexes were found to copolymerize CO and p-methylstyrene affording syndiotactic or isotactic copolymers when bpy or 1,4-(o,o'-dimethylaryl)-1,4-diazabuta-1,3-dienes were used, respectively. The reactions with CO and p-methylstyrene of the bpy derivatives were investigated. Two intermediates derived from a single and a double insertion of CO into the PdÀC bonds were isolated and completely characterized in solution.Introduction. -There is increasing evidence that the solution structure and reactivity of organometallic compounds can be altered by noncovalent interactions. For instance, when ionic compounds are considered, ion pairing may substantially affect the chemical pathway of organic reactions mediated by transition-metal organometallics in terms of chemo-, regio-, and stereoselectivity [1].It has been demonstrated that NMR spectroscopy is the technique of choice for investigating noncovalent adducts in solution, especially by NOE (nuclear Overhauser effect) and PGSE (pulsed-field gradient spin echo) experiments (for recent reviews, see [2]).For several years, our group has been involved in the application of NOE [3a -c] and PGSE [3d] NMR methodologies to determine the interionic structure in solution (namely, the relative cation-anion orientation and aggregation level) of transitionmetal complex ionic adducts. Several combinations of anions (ranging from inorganic, such as [BF 4 ] À and [PF 6 ]

show abstract

Transition‐Metal‐Catalyzed α‐Arylation of Enolates

et al. 2011

View full text Add to dashboard Cite

The aim of this chapter is to present an up‐to‐date overview of the transition‐metal‐catalyzed alpha‐arylation of enolates and their derivatives. This chapter discusses the various efforts to develop highly efficient and selective tools for the catalyzed formation of carbon‐carbon and carbon‐heteroatom bonds. Among the latter, outstanding results have been obtained in the field of soft, non‐organometallic nucleophiles. One of the major challenges is the alpha‐arylation of soft carbon nucelophiles such as stabilized carbon enolates and related functional groups. Although alpha‐carboxylic acids and keto derivatives are prevalent in natural products and are important in the building blocks of various drugs (e.g., anti‐inflammatory drugs, anesthetics, etc.), catalytic alpha‐arylation of stabilized carbon enolates has only been recently described. Details on early research is given. More recent developments of this method concern not only the use of a large number of related nucleophiles, but also activated benzylic and vinylogous gamma‐arylations. Current efforts are mainly devoted to multiple arylation sequences, intramolecular alpha‐arylations, and enantioselective alpha‐arylation. Because palladium is the transition metal predominantly employed, the chapter focuses on palladium‐assisted synthetic transformation, However other catalytic systems such as nickel, copper, and ruthenium‐based catalysts are detailed.

show abstract

Terminal and bridging bonding modes of the acetophenone enolate to palladium(II): the structural evidence and the insertion of isocyanides

Cited by 77 publications

References 0 publications

Transformations of acetone in reactions with carboxylate complexes of palladium

Transformations of acetone in reactions with carboxylate complexes of palladium

Synthesis, Interionic Structure, and Reactivity toward CO and p‐Methylstyrene of Palladacyclic Compounds Bearing α‐Diimine Ligands

Transition‐Metal‐Catalyzed α‐Arylation of Enolates

Contact Info

Product

Resources

About