Metalloligands: Rhodium(III) Cyclometallated Compounds Containing Multitopological Binucleating Ligands

Lanza, Santo; Giannetto, Antonino; Brunò, Giuseppe; Nicolò, Francesco; Tresoldí, Giuseppe

doi:10.1002/ejic.200900165

Cited by 11 publications

(11 citation statements)

References 31 publications

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“…The k 1 form of the N^N donor system is not anticipated to contribute in any way to endo/exo isomerization. Indeed, neither in mononuclear [(η 3 -allyl)Pd(H-meso-(1-phenyl)ethyl-DTO k-S,S Pd)] 2 nor in binuclear [(2-phenylpyridine)Rh(μ-isoamyl-DTO k-N,N Rh k-S,S Pd)Pd(η 3 -allyl)], 10 which contain similar k-S,S Pd systems, has allyl movement been observed.…”

Section: Computational Study All Calculations Were Performed With Thementioning

confidence: 99%

“…9 Furthermore, it has been demonstrated that the hardness or softness of the metal fragments in a heterobimetallic complex produces specific interactions with the sulfur or nitrogen chelating system of the binucleating DTO. 10 Moreover, it has been observed that the steric hindrance of the ancillary ligands in a given metal fragment can also favor the formation of one of the two possible linkage isomers of the k-N,N 0 MLn k-S,S 0 M 0 L 0 n bimetallic complexes. 11 Finally, it has been shown that the bulkiness of nitrogen DTO substituents can direct the synthesis of homobimetallic complexes in an "exo" k-N,S coordination mode toward one of the two possible conformers.…”

Section: ' Introductionmentioning

confidence: 99%

“…Accordingly, it has been observed that DTO, if reacted with some chloro-bridged dimers, forms homobimetallic complexes in a κ-N,S binucleation mode if the amidic nitrogen atoms bear secondary carbon atoms (−CH 2 R) as substituents . Furthermore, it has been demonstrated that the hardness or softness of the metal fragments in a heterobimetallic complex produces specific interactions with the sulfur or nitrogen chelating system of the binucleating DTO . Moreover, it has been observed that the steric hindrance of the ancillary ligands in a given metal fragment can also favor the formation of one of the two possible linkage isomers of the κ-N,N′ MLn κ-S,S′ M′L′n bimetallic complexes .…”

Section: Introductionmentioning

confidence: 99%

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Allylpalladium Dimers with Metals Connected by Binucleating Dithiooxamidates in Two Different Coordination Modes: Solution Behavior and Solid-State Structure

et al. 2011

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A series of allylpalladium dimers having metals connected by binucleating dialkyldithiooxamidate [N(R)SC-CS(R)N](2-) [R = methyl, ethyl, isopropyl, benzyl, isoamyl, (S)-1-(1-phenyl)ethyl, meso-(1-phenyl)ethyl, and rac-(1-phenyl)ethyl] were prepared by reacting the monochelate [(η(3)-allyl)Pd(N(R)SC-CS(R)NH κ-S,S Pd)] with [(η(3)-allyl)PdCl](2) in chloroform. At low temperature (20 °C), the bimetallic complexes [(η(3)-allyl)Pd](2)(μ-dialkyldithiooxamidate κ-N,N' Pd, κ-S,S' Pd') (kinetic compounds) are formed in a short reaction time (10 min). At a higher temperature (50 °C) and a longer reaction time (24 h), the corresponding bimetallic isomers [(η(3)-allyl)Pd](2)(μ-dialkyldithiooxamidate κ-N,S Pd, κ-N',S' Pd') (thermodynamic compounds) are obtained. Both kinetic and thermodynamic compounds can exist as endo or exo isomers, depending on the reciprocal orientation of the allyl cuspids. Both endo and exo isomers are only detectable in solution when the alkyl substituents are chiral alkyl groups. Moreover, diffractometric modeling agrees with the presence of both isomers in the solid state even when the alkyl substituent is an achiral alkyl group. In a chloroform solution, endo and exo isomers undergo isomeric conversion owing to the apparent allyl rotation that follows the Pd-N bond rupture in the (η(3)-allyl)Pd(N^N) frame of kinetic compounds or in the (η(3)-allyl)Pd(N^S) frame of thermodynamic compounds. The dithiooxamidate [N(R)SC-CS(R)N](2-), when engaged in a κ-N,S Pd, κ-N',S' Pd' coordination mode, behaves as a hybrid hemilabile binucleating ligand. At room temperature and in a chloroform solution, the kinetic compounds rearrange into the thermodynamically more stable isomers in about 3 or 4 days. The higher stability of the thermodynamic species was evaluated by means of computational studies in accordance with the maximum hardness principle. Finally, the crystal structures of [(η(3)-allyl)Pd](2)(μ-diethyldithiooxamidate κ-N,S Pd, κ-N',S' Pd'), [(η(3)-allyl)Pd](2)(μ-meso-(1-phenyl)ethyldithiooxamidate κ-N,S Pd, κ-N',S' Pd'), and [(η(3)-allyl)Pd](2)(μ-rac-(1-phenyl)ethyldithiooxamidate κ-N,N' Pd, κ-S,S' Pd') are reported.

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Section: Computational Study All Calculations Were Performed With Thementioning

confidence: 99%

Section: ' Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Allylpalladium Dimers with Metals Connected by Binucleating Dithiooxamidates in Two Different Coordination Modes: Solution Behavior and Solid-State Structure

et al. 2011

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“…Owing to the electronic tunability, modification and ease of synthesis for a wide range of metal ions, the NHCs have been incorporated in a large variety of catalytically active metal complexes [24,25]. Development of new novel class of NHC ligands [26][27][28][29][30] by donor-functionalization, including weak-donor functionalized NHCs (wdf-NHC) have also played an important role in organometallic chemistry and catalysis [31,32]. The C, N-donor NHC ligands can provide considerable benefits due to the extra stability they impart to intermediates in a catalytic reaction [14][15][16].…”

Section: Introductionmentioning

confidence: 99%

Pd(II)–N-heterocyclic carbene complexes of annelated ligand: Synthesis, characterization, and catalytic activity

Rana

Seth²,

Bertolasi

et al. 2015

Inorganica Chimica Acta

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“…which occurs when the metalloligand [(η 3 -allyl)Pd(μ-mesoDTO κ-S,S Pd] splits the chlorido-bridged dimer [Pd(tri n propyl-phosphine)Cl 2 ] 2 .We have recently observed a similar rearrangement of the dithiooxamide ligand on converting the mononuclear metalloligand [(2-phenylpyridine κ-C,N Rh)Rh(H-diisoamyl-DTO κ-S,S Rh)] to the heterobimetallic derivatives [(2-phenylpyridine κ-C,N Rh)Rh(μ-diisoamyl-DTO κ-N,N Rh, κ-S,S M)ML n ] (ML n =(η 3 -allyl)Pd(II), (tri npropyl-phosphine)ClPd(II), (1,5-cyclooctadiene)Rh(I)) 44. Regarding stereochemical features, the bimetallic complexes [[(η 3 -allyl)Pd(μ-mesoDTO κ-N,N Pd, κ-S,S M)M-(PR 3 )Cl] contain two stereogenic elements, namely a pseudochiral palladium atom and a chiral [(mesoDTO κ-S,S M) M (PR 3 )Cl] plane.…”

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confidence: 99%

The Absolute Configuration of Palladium(II) and Ruthenium(II) Pseudochiral Centers in either Chiral or Achiral Environments

Lanza¹,

Nicolò²,

Cafeo³

et al. 2010

Inorg. Chem.

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The meso-dithioxamide H-((R)-1-(1-phenyl)ethyl)-NSC-CSN-((S)-1-(1-phenyl)ethyl)-H (H(2)-mesoDTO) bonds [(η(6)-p-cymene)chlorido-ruthenium(II)](+) or [(η(3)-allyl)-palladium(II)](+) fragment and provides the C(s) symmetrical complexes [(η(6)-p-cymene)ClRu(H-mesoDTO κ-S,S Ru)] (1) and [(η(3)-allyl)palladium(H-mesoDTO κ-S,S Pd)] (2). These complexes are pseudochiral, and each of them exists as a mixture of two symmetrical meso forms. The improper symmetry of [(η(3)-allyl)palladium(H-mesoDTO κ-S,S Pd)] has been broken in two different ways: (i) by changing the symmetrical allyl moiety with a η(3)-crotyl frame or (ii) by substituting the residual amidic hydrogen in the dithiooxamidate ligand with a M(PR(3))Cl(+) fragment (M = Pd or Pt and PR(3) = triorganophosphine). As a consequence, a chiral plane is added to the pseudochiral palladium center, and two pairs of enantiomers are formed in each case. Furthermore, [(η(6)-p-cymene)chlorido-ruthenium(II)](+) and [(η(3)-allyl)-palladium(II)](+) fragments have been joined by means of the binucleating meso-dithiooxamidate ligand in a κ-S,S Ru κ-N,N Pd coordination mode. The resulting C(s)-symmetrical complex [(η(6)-p-cymene)ClRu(μ-mesoDTO κ-S,S Ru κ-N,N Pd)Pd(η(3)-allyl)] (8) possesses two pseudochiral metal centers, and it is therefore a mixture of four isomeric meso forms. All of these isomers in a chloroform solution interconvert in that both palladium and ruthenium invert their configurations. A mechanism of epimerization for both palladium and ruthenium is proposed. The absolute configurations of pseudochiral palladium in [(η(3)-allyl)(c)-Pd(μ-((R)-1-(1-phenyl)ethyl)-NSC-CSN-((S)-1-(1-phenyl)ethyl) κ-N,N (c)-Pd κ-S,S (A,C)-Pd)(A,C)-Pd(tri(n)propyl-phosphine)Cl] (6) and of pseudochiral palladium and ruthenium in [(η(3)-allyl)(c)-Pd(μ-((R)-1-(1-phenyl)ethyl)-NSC-CSN-((S)-1-(1-phenyl)ethyl) κ-N,N (c)-Pd κ-S,S(s)-Ru)(s)-Ru(η(6)-isopropyltoluene)Cl] (8) are provided. A suitable stereochemical notation is proposed for bimetallic complexes containing pseudochiral centers in either a chiral or an achiral environment.

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Metalloligands: Rhodium(III) Cyclometallated Compounds Containing Multitopological Binucleating Ligands

Cited by 11 publications

References 31 publications

Allylpalladium Dimers with Metals Connected by Binucleating Dithiooxamidates in Two Different Coordination Modes: Solution Behavior and Solid-State Structure

Allylpalladium Dimers with Metals Connected by Binucleating Dithiooxamidates in Two Different Coordination Modes: Solution Behavior and Solid-State Structure

Pd(II)–N-heterocyclic carbene complexes of annelated ligand: Synthesis, characterization, and catalytic activity

The Absolute Configuration of Palladium(II) and Ruthenium(II) Pseudochiral Centers in either Chiral or Achiral Environments

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