An Efficient Method for the Synthesis of Boratrane Complexes of Late Transition Metals - Archive ouverte HAL Access content directly
Journal Articles Chemistry - A European Journal Year : 2017

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

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1
Koushik Saha
Rongala Ramalakshmi
  • Function : Author
Rosmita Borthakur
  • Function : Author
Suman Gomosta
  • Function : Author
Kriti Pathak
Sundargopal Ghosh
  • Function : Correspondent author
  • PersonId : 945137

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Abstract

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

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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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