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Article Dans Une Revue Chemistry - A European Journal Année : 2017

An Efficient Method for the Synthesis of Boratrane Complexes of Late Transition Metals

Koushik Saha
Rongala Ramalakshmi
  • Fonction : Auteur
Rosmita Borthakur
  • Fonction : Auteur
Suman Gomosta
  • Fonction : Auteur
Kriti Pathak
Sundargopal Ghosh
  • Fonction : Auteur correspondant
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Résumé

In a quest for efficient precursors for the synthesis of boratrane complexes of late transition metals, we have developed a useful synthetic method using [L'M(μ-Cl)Cl ] as precursors (L'=η -p-cymene, M=Ru, x=1; L'=COD, M=Rh, x=0 and L'=Cp*, M=Ir or Rh, x=1; COD=1,5-cyclooctadiene, Cp*=η -C Me ). For example, treatment of Na[(H B)bbza] or Na[(H B)mp ] (bbza=bis(benzothiazol-2-yl)amine; mp=2-mercaptopyridyl) with [L'M(μ-Cl)Cl ] yielded [(η -p-cymene)RuBH{(NCSC H )(NR)} ] (2; R=NCSC H ), [{N(NCSC H ) }RhBH{(NCSC H )(NR)} ] (3; R=NCS-C H ), [(η -p-cymene)RuBH(L) ] (5; L=C H NS), and [Cp*MBH(L) ] (6 and 7; L=C H NS, M=Ir or Rh). In order to delineate the significance of the ligands, we studied the reactivity of [(COD)Rh(μ-Cl)] with Na[(H B)bbza], which led to the formation of the isomeric agostic complexes [(η -COD)Rh(μ-H)BHRh(C H N S ) ], 4 a and 4 b, in parallel to the formation of 16-electron square-pyramidal rhodaboratrane complex 3. Compounds 4 a and 4 b show two different geometries, in which the Rh-B bonds are shorter than in the reported Rh agostic complexes. The new compounds have been characterized in solution by various spectroscopic analyses, and their structural arrangements have been unequivocally established by crystallographic analyses. DFT calculations provide useful insights regarding the stability of these metallaboratrane complexes as well as their M→B bonding interactions.

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Chimie
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Dates et versions

hal-01685696 , version 1 (16-01-2018)

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Citer

Koushik Saha, Rongala Ramalakshmi, Rosmita Borthakur, Suman Gomosta, Kriti Pathak, et al.. An Efficient Method for the Synthesis of Boratrane Complexes of Late Transition Metals. Chemistry - A European Journal, 2017, 23 (72), pp.18264-18275. ⟨10.1002/chem.201704332⟩. ⟨hal-01685696⟩
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